Minerals Engineering 70 (2015) 178–200

Contents lists available at ScienceDirect

Minerals Engineering
journal homepage: www.elsevier.com/locate/mineng

A review of cassiterite beneficiation fundamentals and plant practices

S.I. Angadi a,⇑, T. Sreenivas b, Ho-Seok Jeon c, Sang-Ho Baek c, B.K. Mishra a
a
CSIR – Institute of Minerals and Materials Technology, Bhubaneswar 751 013, India
b
Mineral Processing Division (MinD), Bhabha Atomic Research Centre, A.M.D. Complex, Begumpet, Hyderabad 500016, India
c
Korea Institute of Geoscience and Mineral Resources, Daejeon 305 350, Republic of Korea

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

Article history: Tin has many important properties and thus it finds wide applications in metal coating, tin plating, alloy-
Received 7 April 2014 ing, soldering, and plumbing, as well as in the electronic, electrical, and organotin compounds industries,
Accepted 16 September 2014 etc. The metal is chiefly produced from the mineral cassiterite, which is generally beneficiated following
Available online 19 October 2014
gravity concentration and flotation techniques. Cassiterite beneficiation has contributed significantly to
the understanding of fundamentals in mineral processing. In particular, the influence of particle size in
Keywords: gravity concentration and flotation techniques has been revealed. Basic research on flotation, such as
Cassiterite
the development of specific surfactants and the adsorption behaviour of these onto mineral surfaces
Gravity concentration
Surfactants
has been performed. In the present review paper, an attempt has been made to summarize the role of
Flotation particulate properties in gravity concentration and adsorption behaviour of flotation surfactants with
Tin beneficiation plants regard to cassiterite. Past tin beneficiation plant practices are reviewed in detail including process
flowsheet developments which have taken place over time.
Ó 2014 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
2. Resources, production and consumption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
2.1. Production . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
2.2. Consumption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
3. Tin minerals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
4. Processing of tin ores . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
5. Gravity concentration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182
6. Flotation and fine particle processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
6.1. Cassiterite surface properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
6.2. Surfactants used in tin flotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
6.2.1. Fatty acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 184
6.2.2. Arsonic acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
6.2.3. Phosphonic and diphosphonic acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
6.2.4. Sulphosuccinamate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
6.2.5. Hydroxamic acids and their tin complexes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
6.2.6. Miscellaneous reagents and methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
6.3. Effect of particle size on tin flotation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 188
6.4. Fine particle processing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
6.5. Recovery from tailings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
7. Beneficiation flowsheets and plant practices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
7.1. Renison, Australia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
7.2. Wheal Jane, UK . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
7.3. Rooiberg and Union Tin Mine, South Africa. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193

⇑ Corresponding author. Tel.: +91 674 2379273.

E-mail addresses: shivakumar_ism@yahoo.com, shivakumar@immt.res.in (S.I. Angadi).

http://dx.doi.org/10.1016/j.mineng.2014.09.009
0892-6875/Ó 2014 Elsevier Ltd. All rights reserved.
 S.I. Angadi et al. / Minerals Engineering 70 (2015) 178–200 179

7.4. Huanuni concentrator, Bolivia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194

7.5. San Rafael, Minsur, Peru . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
7.6. Tin-Tungsten multi-mineral ore, Kyrgyzstan, Central Asia . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
7.7. Uljin deposit, South Korea . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
8. Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198

1. Introduction
The important properties of tin such as malleability, ductility,
and resistance to corrosion make it suitable for use in variety of
applications. Tin was alloyed with copper to form bronze metal
that found wide applications such as making weapons, metal
objects and sculptures and cutting tools during the Bronze Age
(Chakrabarti and Lahiri, 1996). The melting point of the metal is
very low, about 232 °C. When alloyed with lead, the melting point
further reduces to 183 °C, and the alloy is largely used in soldering
in electronic and plumbing applications. The metal finds many
more applications in chemical, alloy making, decorative metals,
etc. The consumption of the metal is rising day-by-day due to
increased end uses.
Cassiterite is the prime mineral from which tin metal is
extracted economically. The mineral is heavy, hard, extremely brit-
tle in nature, and is generally associated with lighter gangue min-
erals. It is reported that about 80% of the world tin reserves are
placer/alluvial deposits (Falcon, 1982, 1985; Wills and Napier-
Munn, 2006, Tin-Indian Mineral Year Book, 2010). Such types of
ores are easy to beneficiate following gravity units due to their
coarse liberation size (Moncrieff and Lewis, 1977). The cassiterite
occurring in hard-rock deposits is associated with granitic host
rock that needs comminution, classification, gravity concentration,
and flotation techniques to beneficiate. The minerals associated
with such types of deposits are harder to beneficiate because of
fine liberation size. Cassiterite beneficiation flowsheets generally
consist of gravity separation units and flotation cells to upgrade
the raw material to a marketable grade concentrate (Collins
et al., 1968; Polkin et al., 1974; Moncrieff and Lewis, 1977; Burt,
1984; Falcon, 1985; Baldauf et al., 1985; Senior and Poling, 1986).
Numerous types of gravity separators are used in the concentra-
tion of tin ores. Units such as jigs, spirals, and tables are used in the
primary concentration stage, and the final concentrate can be
achieved using enhanced gravity concentrators or flotation cells.
Many enhanced gravity concentrators have been developed in
the recent past to address the complex issues of beneficiation.
These enhanced gravity concentrators make use of centrifugal or
other additional forces to increase the separation efficiency. Parti-
cle size plays a major role in gravity concentration (Burt, 1988); the
separation efficiency is very high for coarse particles while it drops
down considerably for fine sizes. The efficiency of different gravity
concentrators treating tin ores has been investigated by many
researchers (Falcon, 1982; Burt, 1984, 1988; Turner and
Hallewell, 1993), and it is reported that advanced gravity concen-
trators could recover particle size down to 3 lm.
A typical gravity concentration circuit recovers about 50–60%
cassiterite (Lepetic, 1987) but significant values in the fine size
are lost in the gravity tailings. Application of flotation and develop-
ment of selective collectors have made it possible to recover fine
cassiterite from the gravity tailings, which has resulted in improve-
ment of overall plant recovery values to over 80%. A substantial
amount of research work on cassiterite flotation has been reported
in the past four to five decades (Polkin et al., 1974; De Cuyper and
Salas, 1977; Lepetic, 1987; Senior and Poling, 1986; Sreenivas,
1997; Sreenivas and Manohar, 1998, 1999, 2000; Sreenivas and
Padmanabhan, 2002; Bulatovic, 2010). During the 1970s, specific
collectors for cassiterite such as arsonic acid, and phosphonic acid
were used in the operating plants; later, the usage ceased due to
economic and environmental concerns. Many more collectors have
been found which are suitable for cassiterite flotation such as oleic
acid, alkyl phosphoric acid, hydroxamates, succinamate phospho-
ric ester, sodiumhylenesulponate and the use of such reagents
has been documented in a number of articles (Lyle and
Shendrikar, 1966; Wottgen, 1969; Moncrieff et al., 1973; Rinelli
et al., 1976; Marabini, 1978; Doren et al., 1979; Kotlyarevsky
et al., 1984; Baldauf et al., 1985; Cheng and Zhu, 1986;
Parsonage and Marsden, 1987; Gruner and Bilsing, 1992;
Khangaonkar and Kamarudin, 1994; Qin et al., 2011; Wang et al.,
2013). The flotation recovery of cassiterite decreases with a
decrease in particle size and in practice ultrafine particles are often
removed prior to flotation. Attempts have been made to recover
such fine and ultrafine cassiterite values following physico-chem-
ical separation techniques such as shear flocculation (Bilgen
et al., 1994), spherical agglomeration (Farnand et al., 1964), selec-
tive flocculation (Clauss et al., 1976), liquid–liquid extraction
(Zambrana et al., 1974) and electro-flotation (Hogan et al., 1979;
Qin et al., 2012; Gonzales et al., 2013), and such attempts are still
in the laboratory scale.
Cassiterite beneficiation plants all around the world have
undergone many developments in terms of modifications in the
conventional flowsheets, incorporation of newly invented equip-
ment, and in revision and adoption of novel chemical reagents,
etc. Most of these developments have been market driven. Several
research articles (Burt and Ottley, 1974; Turner and Hallewell,
1993; Beniuk et al., 1994; Ruiz et al., 2004) highlight implementa-
tion of advanced gravity separators to treat cassiterite fines. Burt
and Ottley (1974) reported the use of the Bartles-Mozley concen-
trator to treat heavy mineral particles; the unit was used to pre-
concentrate cassiterite at Ecstall Mining Ltd., Ontario, wherein tin
values were distributed in all size fractions, and the separator
could recover values down to 10 lm. Falcon (1982) studied the
efficiency of different gravity concentrators treating cassiterite
fines. Turner and Hallewell (1993) discussed in detail plant scale
modifications with respect to reagent scheme, installation of a flo-
tation column, and a Mozley multi-gravity separator in upgrading
the product quality to 60% Sn at the Wheal Jane plant, UK. Simi-
larly, Beniuk et al. (1994) discussed the application of the Kelsey
centrifugal jig in upgrading the product quality and elimination
of the acid leaching plant at the Renison tin concentrator, Australia.
In the current review paper, an attempt has been made to sum-
marize overall developments, which have occurred in gravity con-
centration and flotation techniques for the beneficiation of
cassiterite. The influence of particle size on gravity concentration
and flotation techniques is revisited, and surfactants in cassiterite
flotation are thoroughly reviewed. Tin beneficiation plant practices
are discussed and subsequent improvements in preparing higher
grade concentrates are highlighted.
180 S.I. Angadi et al. / Minerals Engineering 70 (2015) 178–200

2. Resources, production and consumption 350

Tin is 49th most abundant element in the earth crust represent- 300 China
ing 2 ppm, which is lower than zinc, copper, and lead (Emsley, Indonesia
250

Production '000 tonnes

2001). Cassiterite is an abundant tin mineral of economic impor-
tance; it occurs in alluvial/placer deposits as well as primary
hard-rock deposits (Falcon, 1982). Tin occurrence in alluvial/placer
deposits is due to weathering of primary hard-rocks followed by
transportation of eroded material. The heavy and chemically resis-
tant tin easily form residual concentration and such deposits are
mostly located in South East Asian continents, particularly in
Malaysia, Indonesia and Thailand. The primary hard-rock deposits
are of late-stage granitic intrusions found in veins and fissures in
the granite and surrounding country rocks. The hard-rock deposits
are predominant in China, South America and Australia.
The estimated tin metal resources in the world is about 4.9 mil-
lion tonnes, which is distributed in China (30.5%), Indonesia
(16.3%), Brazil (14.5%), Bolivia (8.1%), Russia (7.1%), Peru (6.3%),
Malaysia (5.1%), Australia (4.9%), and Thailand (3.5%) (Mineral
commodity summaries, 2013). Table 1 summarizes the world mine
production and distribution of tin.
2.1. Production
The strategic metal tin production was almost stable at about
200 tonnes per annum during the post-war period and finds many
ups and downs in 1960–1990 due to fluctuations in the interna-
tional market price. The world production of tin reached as high
as 325,000 tonnes in 2005 due to increased demand. Around
244,000 tonnes of tin production reported in 2011 of which about
80% comes from China, Indonesia and Peru. World reserves and
mine production of different countries is presented in Table 1.
Fig. 1 shows the world mine production from 1970 to 2010. It
can be observed from the figure that the refined tin metal produc-
tion varies year by year with respect to different countries, but
average production from all countries shows an increasing trend.
The cumulative production of maximum tin accounts for China,
Indonesia, Brazil, Bolivia, and Peru. Since the 1990s, there is no
report of smelting of tin metal from US and European producers.
About 15% of the world production accounts from the secondary
materials that reports from Belgium and China.
2.2. Consumption
Tin consumption by different sectors is varying with time. Tin
plate industries in USA and European countries consume the major
Brazil
Bolivia
200
Russia
150 Peru
Malaysia
100 Australia
Thailand
50
Others
0
1970 1975 1980 1985 1990 1995 2000 2005 2010
Year of production
Fig. 1. Tin world mine production 1970–2010 (ITRI Briefing, 2011).
quantity of tin during 1970s, while the consumption rate remained
constant and/or declined in 2000. Since 2000, consumption of tin
increased in electronic soldering applications in Asian countries,
particularly in China and Japan. The solder industries have con-
sumed about 52% of the tin produced followed by tin plates and
chemical industries during 2006. It is reported (ITRI Briefing,
2011) that world consumption of tin from 1960 to 2000 main-
tained a plateau of 200,000–250,000 tonnes and 2000 onwards it
has raised to 350,000 tonnes.
3. Tin minerals
Tin is preferentially concentrated during magmatic differentia-
tion process and shows affinity for granitic rocks and their extru-
sive equivalence. Table 2 shows the list of tin minerals that occur
in the earth crust, of these the only economic mineral is cassiterite
(SnO2). The physical and chemical properties of cassiterite are
given in Table 3. The economic deposits of cassiterite are known
in two types of geological occurrences – primary vein or hard-rock
deposits and secondary placer deposits (Falcon, 1982; Rao, 1992).
The mineral assays about 0.4–1.5% Sn (occasionally 5–6%) in the
hard-rock deposits and placer deposits are slightly poorer in grades
(Bulatovic, 2010). Pure cassiterite theoretically accounts 78% Sn.
Typical concentrate grades vary between 65% and 78% Sn contents
due to the presence of various mineral impurities containing the
elements such as tantalum, niobium, titanium and others.
Cassiterite occurring in the placer type deposits is often coarse
grained and physically liberated state (Moncrieff and Lewis, 1977).

Table 1
World mine production and reserves of tin (Mineral commodity summaries, 2013).

Country Mine production (tonnes) Reserves (tonnes) % Distribution of reserves

2011 2012
Australia 6500 6000 240,000 4.9
Bolivia 20,300 20,000 400,000 8.1
Brazil 11,000 11,500 710,000 14.5
China 120,000 100,000 1,500,000 30.5
Congo (Kinshasa) 2900 5700 NA
Indonesia 42,000 41,000 800,000 16.3
Malaysia 3350 3300 250,000 5.1
Peru 28,900 29,000 310,000 6.3
Russia 160 160 350,000 7.1
Rwanda 1400 3600 NA
Thailand 200 300 170,000 3.5
Vietnam 5400 5400 NA
Other 2000 2000 180,000 3.7
Total 244,110 227,960 4,910,000 100.0
 S.I. Angadi et al. / Minerals Engineering 70 (2015) 178–200 181

Table 2 arsenopyrite, marcasite, sphalerite and galena in silicate-carbonate

List of tin minerals. gangue. In many hard-rock deposits cassiterite and stannite are
Mineral Chemical formula Specific gravity associated with complex polymetallic sulphide ores. Beneficiation
Silicates of such ores is difficult since stannite behaves similar to pyrite
Pabstite Ba(Sn,Ti)Si3O9 4.03 and other sulphide minerals during various processing stages
Malayaite CaSnO[SiO4] 4.3–4.55 (Benzaazoua et al., 2003; Xu et al., 2012).
Arandesit 3SnSiO42SnO24H2O 4.0 Cassiterite occurrences in placer and hard-rock deposits are
Stokezit H2CaSnSi3O11 3.2
Boratin SnO26B2O35H2O 4.3
very distinct. Hence, different mining methods are employed for
the extraction. Primary hard-rock deposits are intrusions found
Oxides
Cassiterite SnO2 6.98–7.1
in the granite and surrounding country rocks, whereas, secondary
alluvial/placer deposits are formed due to weathering of earlier
Sulfides
Canfieldite Ag8SnS6 6.28
rocks and transportation to redeposit along with the sediments
Kesterite Cu2(Zn,Fe)SnS4 4.54–4.59 (Falcon, 1982). Mining methods such as bucket-line dredging,
Stannite Cu2FeSnS4 4.3–4.5 gravel-pump operations are used for placer deposits in addition
Mohite Cu2SnS3 4.86 to hydraulicking and various open pit methods. For vein type
Teallite PbSnS2 6.4
deposits, methods similar to hard-rock mining are usually adopted
Cylindrite Pb3Sn4FeSb2S14 5.4–5.42
Franckeite (Pb,Sn2+)6Fe2+Sn2Sb2S14 5.88–5.92 (ITRI Briefing, 2012).
Colusite Cu3(As, Sn, V, Fe, Te)S4SnS 4.4–9.6 Generally, beneficiation flowsheet for tin ores includes a combi-
Herzen bergite SnS nation of gravity and flotation units. In placer deposits, cassiterite
Chlorites occurs in a liberated state thus comminution is not required for the
Abhurite Sn3O(OH)2 Cl2 beneficiation. Because of high specific gravity, chemical stability
Borates and resistance to abrasion, cassiterite is concentrated using gravity
Tusionite MnSn(BO3)2 4.73 separators. The up-gradation circuit configuration depends on the
Nordenskioldine CaSnB2O6 4.2 type and nature of gangue minerals associated with the tin values.
In general, the up-gradation section consists of gravity, electro-
World’s major tin output is from placer deposits that are located in static, magnetic and flotation (to remove sulphide minerals) tech-
Brazil, Thailand, Indonesia and Malaysia. The hard-rock deposits niques, either individual units or in a combination (Bulatovic,
are associated with granite rocks particularly greissenised granites. 2010). About 80% of the tin produced from the alluvial/placer
The cassiterite in load type deposits is highly disseminated and deposits are mainly located in the South East Asian continent.
intimately associated with other minerals. Major tin producers The disseminated nature of cassiterite occurrence in lode type
from lode type deposits are China, Bolivia, Peru, Australia, South deposits necessitates fine grinding to liberate mineral values from
Africa, UK, Germany and Canada (Bulatovic, 2010). the host rock (Moncrieff and Lewis, 1977). The inherent brittle nat-
ure of cassiterite leads to the generation of undue fines not only
4. Processing of tin ores during grinding but also during various other processing stages.
The recovery of fine particles is a difficult process. It is a common
Cassiterite is the prime tin mineral present in the earth crust practice in tin beneficiation to recover the mineral as coarse size
followed by stannite, kesterite, mawsonite, and other tin sulphides as possible, which necessitates implementation of multi-stage pro-
(Benzaazoua et al., 2003; Xu et al., 2012). The importance of min- cessing routes (Falcon, 1982). Many lode type tin mines use various
eralogy in the beneficiation of tin ores is reported by many pre-concentration units either before or after primary grinding
researchers (Holl and Bromley, 1988; Veasey et al., 1989; stage. The pre-concentrate thus obtained is reground, classified
Benzaazoua et al., 2002, 2003; Xu et al., 2012). These research arti- and processed through appropriate gravity machines. Further
cles outline the role of geological factors, mineralogy, texture, and cleaning of the concentrate can be achieved following similar tech-
mineral association in flowsheet development as well as in niques that are used in the placer tin processing. Generally, gravity
improving performance of the existing plants. Carbonate-replace- concentrators (spirals and tables) are used to recover cassiterite
ment (skarn) tin deposits represent world’s major exploration sites particles >30 lm. However, recovery by gravity machines becomes
for primary tin ores (Kitto, 1998). Cassiterte mineralisation in these gradually difficult as the particle size reduces to finer size. The per-
replacement deposits occur in fine grained and closely associated formance data of many operating tin plants indicate a loss of about
with sulphide minerals such as pyrrhotite, chalcopyrite, pyrite, 30–40% cassiterite values in the gravity tails (Lepetic, 1987). Efforts

Table 3
Physical and chemical properties of cassiterite (Blackburn and Dennen, 1988).

Physical and chemical properties Details

Chemical formula SnO2
Sn content in pure SnO2 78%
Crystal structure Tetragonal
Cleavage planes Imperfect {1 0 0}, Distinct Parting on {1 1 1} or {0 1 1}. Subconcochoidal to uneven fracture
Specific gravity 6.8–7.1
Hardness Brittle
Tenacity Subadamantine to submetallic
Optical Transparent to opaque
Colour Brown or black, rarely gray, red, white or yellow
Optical x = 2.006,  = 2.097; positive
Lattice constants (Å) a = 4.738, b = 3.188
Strong X-ray diffraction lines (Å) 3.351 (100), 2.644 (81), 1.765 (63)
Magnetic property Non-magnetic
Occurrence Characteristically found in high-temperature hydrothermal veins or contact metamorphic deposits
genetically related to quartzose igneous rocks. Also noted in pegmatites and as an accessory mineral in acid igneous rocks
182 S.I. Angadi et al. / Minerals Engineering 70 (2015) 178–200

are made to recover these lost values using state of the art fine iii. Shaking devices: (f) Shaking table; (g) Bartles–
gravity machines such as Bartles Mozley separator (BMS), Bartles Mozley; (h) Crossbelt
cross belt concentrator (CBC) and more recent Mozley multi-gravity iv. Air devices: (i) Pneumatic jig; (j) Air table
separator (MGS) and Falcon Ultra-Fine centrifugal concentrator v. Miscellaneous devices: (k) Centrifugal separators
(Burt, 1984, 1988; Mozley and Childs, 1992). However, many plants
consider flotation of tin using specific collectors because of the
advantages like higher tin selectivity and recovery (Foo et al., 1983).

In stratification devices, separation of particles is imparted due

5. Gravity concentration
to pulsation and suction offered by the fluid in a vertical plane. In
the category of flowing film devices, separation is achieved due to
Gravity concentration is an age-old method used in the mineral
differential motion of particles flowing along with the fluid down
processing plants for the separation of heavy and light mineral par-
the inclined surface. This principle is used in sluice, pinched sluice,
ticles. Importance of this technique has been reduced due to the
Reichert cone, and spiral units. In shaking table, Bartles–Mozley
invention of flotation (Burt, 2000), which is more efficient and
separator and crossbelt concentrator, density separation is
applicable to a wide variety of ore minerals. In spite of this, large
imparted due to superimposition of horizontal or orbital shear
quantity of ores beneficiated using gravity concentrators because
along with the flowing film concentration. Water is used as a sep-
of low processing costs and environmental friendly operations
arating fluid in the above mentioned devices, whereas, air is used
(Richards et al., 2000). At present, gravity separation equipments
instead of water in pneumatic jigs and air tables. Many new types
are prime concentrating units in the beneficiation of coal, iron
of equipments are designed in the recent past with the intension to
ore, heavy mineral sand, gold, barite, fluorspar, tin, tungsten, etc.
increase gravitational force by integrating centrifugal action. The
Beniuk et al. (1994) reported that majority of tin produced at Ren-
centrifugal separators are very well accepted in the treatment of
ison plant is from the gravity circuit.
fine to ultra-fine particles.
Gravity concentration technique is inevitable for tin beneficia-
Separation characteristics and particle size handling in each
tion, since heavy mineral cassiterite is associated with lighter gan-
gravity unit is different. Fig. 2 shows working particle size range
gue minerals. Use of pan, sluice box and pinched sluice for the
of gravity concentration equipments discussed in the above
beneficiation of placer tin old workings are reported by many
paragraph.
researchers (Falcon, 1982; Earl and Ozbal, 1996). Literature also
Burt (1984) reported that slimes gravity concentrators can han-
reports various types of gravity separators such as jig, heavy media
dle the particle size as coarse as 45–53 lm. On the other hand,
cyclone, spiral, shaking table, multi-gravity separator, Bertles–
such units are not efficient to recover particle size finer than
Mozley separator, cross-belt separator, Falcon Ultra-Fine centrifu-
5 lm. Gravity concentration is sensitive to the particle size. Fine
gal concentrator, etc. in the concentration of tin ores. A lot of
particles possess small mass as a result momentum of the particles
improvements have been achieved in the gravity concentration
decreases and takes long time to separate in the gravity units. Such
over the years. Many new types of equipments have been devel-
particles also exhibit large surface area resulting into increased vis-
oped for the treatment of fine and ultra-fine particles. The working
cosity of the fluid or in other words declined separation efficiency.
principle of all these newly invented units is a density separation
The efficiency of gravity separators for treating tin-tungsten-
along with different force field environment i.e. two or more forces
tantalum type of ores is reported by Burt (1984). Fig. 3 shows
are involved in the separation along with a density. Based on these
the gravity separation efficiency with respect to particle size. It
differences Burt (2000) has classified gravity concentrators into the
can be observed from the figure that the fine gravity separators
following category.
are efficiently processing particle size 40–5 lm. The separation
i. Stratification devices: (a) Jig efficiency reduces with the decrease in particle size. Table 4 shows
ii. Flowing-film devices: (b) Sluice box; (c) Reichert cone; performance of various gravity concentrators treating fine tin ores
(d) Pinched sluice; (e) Spiral (Burt (1988)). It can be observed from the table that crossbelt

(A) Stratification devices: (a) Jig

b (B) Flowing-film devices: (b) Sluice box

(c) Reichert cone
c (d) Pinched sluice
(e) Spiral
d
e

100.0 10.0 1.0 0.1 0.01 f (C) Shaking devices: (f) Shaking table
Particle size in mm g (g) Bartles-Mozley
(h) Cross belt
h

i
k j (D) Air devices: (i) Pneumatic jig
(j) Air table

(E) Miscellaneous devices: (k)centrifugal separators

Fig. 2. Working range of gravity concentration equipments.

 S.I. Angadi et al. / Minerals Engineering 70 (2015) 178–200 183

in the fines should be above 0.1% by weight. The concentrator gen-

erates centrifugal force up to 600 times the force of gravity (600
G’s) and finds efficient in the processing of cassiterite, tantalum
and scheelite minerals. The Falcon UF device can be used as an
alternative unit to de-slime feed to the flotation cells. In Renison
tin mine Falcon UF 1500 device is introduced in place of a Mozley
gravity separator to enrich the flotation concentrate from 15% to
40% Sn.

6. Flotation and fine particle processing

Flotation is a physico-chemical method of separation of hydro-

Fig. 3. Recovery-size curve for fine gravity separators (Burt, 1984).
concentrator, Bartles-Mozley separator, and slime table are very
efficient for the beneficiation of tin ores.
Selection of processing units for the beneficiation of tin ores is
very important (Jeon et al., 2012). It is reported that one-third of
tin mined in Bolivia is wasted in plant tailings (A Bandopadhyay,
2000), which is mainly attributed due to lower efficiency of the
gravity concentrators and flotation units in treating ultrafine tin.
Turner and Hallewell (1993) described metallurgical improve-
ments achieved due to insertion of Mozley multi-gravity separator
as the final stage of cleaning in place of existing flotation column at
Wheal Jane plant UK. The multi-gravity separator was capable of
recovering fine cassiterite values in the size range 45–6 lm. Details
of Wheal Jane plant operations are discussed in the subsequent
sections.
The rocking shaking vanner was developed in China (Chin et al.,
1979) for the beneficiation of tungsten, tin and other rare metallic
ores. It is reported that this equipment finds applications in clean-
ing of middlings and rougher concentrates, and also it is capable to
separate particle size down to 20 lm and finer.
Snþ4 ðliqÞ þ 4OH
Rao and Subrahmanyan (1986) reported that significant amount
of tin mined in South Asian continent is lost in the gravity concen-
tration tailings. Many developments in the gravity concentration
equipment design have been observed during 70s and 80s for
treating fine to ultrafine particles. The units such as Bartles–Moz-
ley separator, Bartles cross-belt separator, Mozley multi-gravity
separator, Falcon UF separator etc. were found efficient in the ben-
eficiation of fine tin particles.
Falcon Ultra-Fine (UF) separator is used for the concentration of
heavy minerals present in the ultra-fine (up to 3 lm) particles
SnðOHÞ4
(Kroll-Rabotin et al., 2013). Generally, the heavy mineral content
phobic and hydrophilic particles. The fundamental studies on flota-
tion involve the components such as (a) electro-chemical studies of
the mineral surfaces – solubility and other physical properties (b)
surfactant functional groups – physical and electro-chemical prop-
erties, complexation behaviour and (c) pulp chemistry – types and
concentrations of various electrolytes, influence of pH and hydro-
dynamic factors (Attia and Fuerstenau, 1978). In the present
review, fundamental components pertaining to the cassiterite flo-
tation are discussed in detail.
6.1. Cassiterite surface properties
The chemical formula of cassiterite is SnO2. It possesses a
tetragonal structure, 6:3 coordination with oxide anions arranged
in octahedral around a stannic ion (Wells, 1975; O’Connor and
Buchanan, 1953). Pure cassiterite is almost chemically inert, and
is highly insoluble i.e. the concentration of constituent ions in solu-
tion is negligible (Edwards and Ewers, 1951; Kragten, 1975;
Barsukov and Klintsova, 1970; Klintsova et al., 1973) as shown in
Table 5.
Cassiterite, when placed in aqueous medium undergoes
hydroxylation as shown below:
SnO2.nH2O(solid)
Sn(OH)6-2 Sn(OH)5- Sn(OH)4 Sn(OH)3+ Sn(OH)2+2 Sn(OH)+3 Sn+4
SnO2 ðcrystallineÞ þ 2H2 O ðliqÞ
The equilibrium constant, pK298.15, of the reaction is reported as
59.7 ± 0.5. The equilibrium constant for freshly precipitated tin
hydroxide at 20 °C is reported to be 56, and for the aged tin
hydroxide it is 61.
From the investigations on the solubility of stannic oxide in
water at 25 °C, it was found that in the pH range 2–11 solubility
does not depend on the pH and a neutral molecule is formed that
dissolves, which is shown below:
SnO2 þ 2H2 O

Table 4
Performance comparison of various gravity concentrators treating fine tin ores (Burt, 1988).

Equipment Assay (%) Recovery (%) Enrichment ratio Capacitya

Feed Conc.
Vanner 0.58 4.95 19.0 8.53 0.67
Denver Buckman 0.81 4.01 40.0 4.95 10.80
B M separator 0.49 1.52 70.0 3.1 12.40
Y T centrifugal 0.40 1.10 80.0 2.75 13.00
Crossbelt concentrator 0.36 31.76 52.5 88.20 1.30
GEC duplex 0.34 10.51 51.3 30.91 4.00
Rocking vanner 0.34 11.00 68.0 32.90 0.35
Spiral sluice 0.31 6.77 40.0 21.80 48.00
Slime table 0.35 13.37 55.4 38.20 0.87
a
Capacity in tons per day per square metre of floor space.
184 S.I. Angadi et al. / Minerals Engineering 70 (2015) 178–200

Table 5 A list of collector reagents used in the flotation of cassiterite

Solubility of cassiterite in water at 25 °C. with their properties, and applications are tabulated in Table 6.
pHa Sn+4 (lg/ml) Collectors play a vital role in the selectivity of any flotation process.
2.0 0.030 The role of modifiers cannot be undermined, particularly when the
5.7 0.066 valuable mineral is in association with many similar floating min-
7.0 0.021 erals. Some of the minerals that occur along with cassiterite in a
9.0 0.026 typical lode type ore deposits are pyrite, chalcopyrite, pyrrhotite,
10.0 0.045
11.0 0.046
iron oxide, garnet, tantalite, wolframite, scheelite, apatite, mona-
zite, barite, fluorite, spodumene, zircon, topaz and tourmaline
a
pH adjusted with dil HNO3 and NaOH. (Sreenivas, 1997). Among these, the floatability of cassiterite was
found to be similar to topaz, tourmaline (Andrews, 1991), iron oxi-
des and wolframite (Collins et al., 1968; Abeidu, 1975). The most
the pK of this reaction is 6.44 ± 0.25. frequently used depressants and dispersants are sodium silicates,
The stability constants of hydroxyl complexes of Sn(IV) at ionic sodium fluoride and sodium silico fluoride. The former depresses
strength 1.0 and at 25 °C are: various types of silicate gangue and is also a good dispersant help-
ful in improving grades. The latter two modifiers are said to be
Snþ4 þ H2 O
SnðOHÞþ3 þ Hþ K 1 ¼ 3:73 helpful in controlling flotation of tourmaline and fluorite. In Boliv-
ian tin plants depression of tourmaline was achieved by citric acid,
SnðOHÞþ3 þ H2 O
SnðOHÞþ2
2 þH
þ
K 2 ¼ 1:29 while oxalic acid was favoured in many Russian plants (Arbiter,
1977; Bogdanov et al., 1973). These organic acids are also used to
regulate pH and sequester the undesired metal ions in the flotation
SnðOHÞþ2 þ
2 þ H2 O
SnðOHÞ3 þ H
þ
K 3 ¼ 0:47
pulp. Poly phosphates are known to depress not only phosphatic
gangue but also to bring selectivity between cassiterite and wol-
SnðOHÞþ3 þ H2 O
SnðOHÞ4 K 4 ¼ 0:06 framite (Abeidu, 1974). In many cases, it was found that sulfuric
acid performs a dual role of pH regulator and depressor for some
It follows from this that Sn(OH)4 will predominate in solutions
silicate minerals. Experience in many operating plants shows that
with pH > 1.2. The distribution of tin (IV) hydroxide complexes as a
the use of these modifiers should be judicious, as anything in
function of pH is given in Fig. 4.
excess is detrimental for the flotation of cassiterite (Parsonage
and Marsden, 1987).
6.2. Surfactants used in tin flotation Many of the collector reagents used in cassiterite flotation have
been observed to produce good frothing characters (like phos-
Extensive fundamental and applied research on flotation of phonic acid, sulfosuccinamate) depending on the pH of the pulp.
cassiterite is reported in the literature (Lyle and Shendrikar, Presence of ultrafine particles in the pulp results into excessive
1966; Wottgen, 1969; Moncrieff et al., 1973; Polkin et al., 1974; and tough froth. Hence it is a common practice in many tin plants
Rinelli et al., 1976; De Cuyper and Salas, 1977; Marabini, 1978; to efficiently deslime the feed prior to flotation. Literature also
Doren et al., 1979; Kotlyarevsky et al., 1984; Baldauf et al., shows (Lepetic, 1987) that the performance of cassiterite plants
1985; Cheng and Zhu, 1986; Lepetic, 1987; Senior and Poling, has improved on switching over to an appropriate collector-frother
1986; Parsonage and Marsden, 1987; Gruner and Bilsing, 1992; combination that helped in obtaining better froth structure. Some
Khangaonkar and Kamarudin, 1994; Sreenivas, 1997; Sreenivas of the industrially used frothers are methyl isobutyl carbinol
and Manohar, 1998, 1999, 2000; Sreenivas and Padmanabhan, (MIBC), Dowfroth 250 or Aerofroth 250.
2002; Bulatovic, 2010; Qin et al., 2011; Wang et al., 2013). The
outcome of such research has helped to develop various collector 6.2.1. Fatty acids
reagents such as cupferron, sodium oleate, sodium cetyl sulfate, The earliest recorded work on flotation of cassiterite was pub-
sodium dodecyl sulfate, petroleum sulfonate, alkyl and aryl phos- lished in 1930s (Collins et al., 1968). The usage of fatty acids and
phonic acids, alkyl arsonic acids, dicarboxylic acids, diphosphonic soaps as a collector and a variety of depressants, including sodium
acid, alkyl sulfosuccinamates, salicyaldehyde, phosphoric acid silicate, hexametaphosphate, lactic acid, tannium, metal salts and
esters and alkyl hydroxamates. acids in improving flotation selectivity are reported. A more sys-
tematic work on interaction of oleic acid and cassiterite is made
by Russians (Polkin et al., 1974, 1967). They concluded that pure
cassiterite is more responsive to oleate flotation than many non-
sulfide minerals. The presence of impurities in the crystal lattice
increases the collector adsorption density, on the contrary,
decreases the flotation recovery. Flotation of cassiterite occurs
with less than a monolayer of oleic acid. Usual consumption of
oleic acid is about 1 kg/ton and has shown suitability for simple
ores and ores containing quartz as a gangue mineral. Baldauf
et al. (1985) studied the application of alkane dicarboxylic acids
for cassiterite flotation. The special features noted by the authors
are the ability of dicarboxylic acids to float relatively coarse (about
100 lm) cassiterite particles, and low reagent requirement com-
pared to oleic acid and other established cassiterite collectors.
When studied on a mixture of cassiterite and topaz (commonly
occurring gangue in tin ores), the selectivity of the reagent was
unsatisfactory. The flotation performance improved on the addi-
Fig. 4. Distribution of tin (IV) hydroxyl species at different pH conditions at room tion of amino-naphtholsulfonic acid depressant along with dicar-
temperature (Klintsova et al., 1973). boxylic acid.
 S.I. Angadi et al. / Minerals Engineering 70 (2015) 178–200 185

Table 6
Summary of various collector reagents used in cassiterite flotation.

Reagent/(Refs.) Chemical formula Ionisation pKa Studies Application

Cupferron (Vivian, 1927) C6H5N(NO)(ONH4) Weak acid Flotation Laboratory investigations on natural ore
Salicyaldehyde (Marabini, 1978) C6H5OHCHO Strong acid Flotation and Laboratory investigations on pure mineral
Adsorption and natural ore
Hydroxamic Acids (Gorlvoskii et al., RCONHOH or RCONHOK Weak acid Flotation Laboratory and pilot plant investigations
1968)
Sulfo-succinamate (Senior and Poling, CH2COONa Di-basic acid pK1 = 2.3 Flotation and Laboratory and plant investigations
1986) pK2 = 5.8 adsorption
COONa CHCOONa
CH-CH2-CO-N

SO3Na C18H37

Arsonic acid (Senior and Poling, 1986) OH Weak di-basic acid Flotation and Laboratory and plant investigations
pK1 = 3.77 pK2 = 8.73 adsorption
R-As O when
OH
when R = CH3C6H5
R = CH3C6H5
Alkyl and aryl phosphonic acid (Senior OH Weak di-basic acid Flotation and Laboratory and plant investigations
and Poling, 1986) pK1 = 2.0 pK2 = 7.1 adsorption
R-P O when
OH
when R = C6H5(C2H3)
R = C6H5(C2H3)
Di-phosphonic acid (Kotlyarevsky PO3H2 Weak di-basic acid Flotation Laboratory investigations on pure mineral
et al., 1984) and natural ore
R-C OH

PO3H2
Oleic acid (Polkin, 1960) CH3(CH2)7 = CH(CH2)7COOH Weak acid pK = 4.7 ± 0.5 Flotation and Laboratory and plant investigations
adsorption
Sodium cetly sulphate (Edwards and R-SO4Na Strong acid Flotation and Laboratory investigations on pure mineral
Ewers (1951)) adsorption
Di-carboxylic acid (Baldauf et al., 1985) COONa Weak acid Flotation Laboratory investigations on pure mineral
and synthetic mixture

C10H21 CH

COONa
Alkylphosphorous acid easter (Cheng OH Strong acid Flotation and Laboratory investigations on pure mineral
and Zhu, 1986) adsorption and natural ore

R O P O

OH

6.2.2. Arsonic acids
The identification of p-tolyl arsonic acid as a selective collector
for cassiterite was a major catalyst to introduce flotation in many
tin mines around the world (Senior and Poling, 1986). The com-
mercial production of this reagent was ceased in the free world
market after 1975 due to its high cost and environmental concern.
However, the high selectivity of arsonic acid based reagents for
cassiterite made it suitable to be used even now in cassiterite flo-
tation plants in China in the form of MTAA (50:50 mixture of o-
and p-toly arsonic acid). The optimum pH for flotation with arsonic
acid is generally laying in the region pH 3.7 to 8.5. An unusual fea-
ture of the arsonic acid flotation is its inability to recover particles
coarser than 40 lm.
6.2.3. Phosphonic and diphosphonic acids
A significant advancement in cassiterite flotation has been the
development of new class of collectors – the alkyl and aryl phos-
phonic acids. It was established by Kirchberg and Wottgen
(1964) that of various aryl compounds tested, p-ethyl benzene
phosphonic acid was the most efficient. Optimum results were
obtained with the alkyl phosphonic acids of chain length C5–C7
(Wottgen, 1969). The work by Collins et al. (1968) concluded that
aryl phosphonic acids are more selective compared to alkyl phos-
phonic acids. The microflotation studies indicated that maximum
cassiterite recovery observed with phosphonic acid collectors
between pH 2 to 3, which decreases rapidly at lower pH. The flota-
tion response gradually decreases from pH 3 to 7, beyond pH 7 it
drops rapidly. However, plant experience showed interruptions
in flotation below pH 4 (Senior et al., 1989). It was observed that
phosphonic acids are efficient at particle size finer than 40 lm
and are also efficient for cassiterite that occurs along with high iron
content.
Kotlyarevsky et al. (1984) synthesised and tested a variety of
substituted diphosphonic acids for cassiterite ores. These authors
used p-electron donor compounds with low polarity to enhance
the hydrophobicity in conjunction with diphosphonic acids. Based
on their results it was found that 1-hydroxyalkylidene-1, 1-diphos-
phonic acid (Flotol-7, 9) with 7–9 carbon atoms produced best col-
186 S.I. Angadi et al. / Minerals Engineering 70 (2015) 178–200
lection properties for cassiterite. Flotol-7, 9 exhibits a wide range
of differentiation in terms of collecting properties for cassiterite
and other rock forming minerals (tourmaline, ferrous oxide and
garnet). In addition, unavoidable ions in flotation pulp such as tri-
valent iron and aluminium have a negligible effect on cassiterite
flotation with Flotol-7, 9. Flotation experiments on an ore contain-
ing 0.56% Sn with Flotol-7, 9 gave a concentrate analyzing 25.6% Sn
with 83% recovery. Other cassiterite collectors (styrene phosphonic
acid, sulphosuccinamate and hydroxamic acid) gave equal recovery
with much inferior concentrate grade. The reagent consumption in
the case of Flotol-7, 9 is less, by half, compared to other collectors.
Similar performance was observed by Houot and Desbrosses
(1991) when tested on a complex sulphide polymetallic ore con-
taining 5.8% Sn. About 50% of cassiterite was recovered with a con-
centration ratio of 12, using 400 g/t of dodecane diphosphonic acid
at pH 5.
Gruner and Bilsing (1992) reported the use of styrene phos-
phonic acid in the laboratory flotation of different tin ores collected
from Czechoslovakia, Canada, Portugal and Germany. Also, this
reagent has been introduced into the processing plants at Neves
Corvo, Portugal, Rio Kemptville, Canada and Altenberg, and Ger-
many. The results show that styrene phosphonic acid is suitable
for the flotation of finely disseminated cassiterite and wolframite
ores, and it is possible to obtain a high-grade concentrates of more
than 40% Sn with high recovery values.
6.2.4. Sulphosuccinamate
The first recorded use of sulfosuccinamate as a collector for cas-
siterite was at Wheal Jane concentrator, Cornwall, UK (Senior and
Poling, 1986; Lepetic, 1987). While the selectivity of the reagent
was inferior to arsonic acid, it was less toxic, biodegradable and
cheaper than arsonic acid, which led to its wide-spread usage in
many plants. In his original patent, Arbiter (1968) stated that flota-
tion of cassiterite with sulfosuccinamate was best carried out at pH
value < 2.5, and that is a pH well below the isoelectric point of cas-
siterite. Published micro-flotation test results (de Cuyper and Salas,
1977; Zambrana et al., 1974) confirm that recovery reaches a max-
imum well below the cassiterite isoelectric point and drops signif-
icantly when the zeta potential of the mineral decreases and
becomes negative in sign. However, Khangaonkar and Kamarudin
(1994) have observed good flotation in the pH range of 2–10, when
the grain size of cassiterite is between 75 and 106 lm. In industrial
flotation pulps high recoveries can be expected at pH > 2.5
(Moncrieff et al., 1973) presumably due to the ability of various
ions inevitably present in the flotation pulps that adsorb on the
cassiterite surface and increase the pH range over which the min-
eral surface is positively charged.
Fig. 5. Dissociation equilibria of hydroxamic acid in water, R – aryal or alkyl group (Shenderovich et al., 1979).
6.2.5. Hydroxamic acids and their tin complexes
Hydroxamic acids are regarded as derivatives of both hydroxyl
amine and carboxylic acids, which can be represented by the gen-
eral formula ARACOANHOH (Yale, 1943; Agarwal, 1979; Brandt,
1960). A striking feature of hydroxamic acids is their ability to form
coordination compounds (Chatterjee, 1978). As a bidentate group,
the anionic hydroxamate resembles the acetylacetonato ligand,
CH3ACOACH2ACOACH3, in its behaviour towards various metal
ions. The pKa of the usual alkyl hydroxamic acid is close to 9
(Ryaboi et al., 1980). It has been established that the protons disso-
ciate from the oxygen attached to nitrogen, giving the structure of
hydroxamate anion, RCONHO (Fuerstenau, 1984). However few
researchers (Exner, 1968) have reported that most of the hydroxa-
mic acids belong to the N-acid type rather than O-acid type; i.e.,
the hydrogen attached to the nitrogen atom is acidic than the
one attached to the oxygen.
According to the existing concepts, hydroxamic acids can disso-
ciate in accordance with the scheme given in Fig. 5 (Shenderovich
et al., 1979). Existence of the forms III and IV has been shown most
convincingly for benzohydroxamic acid in solution, in all other
cases these forms have merely been regarded as possible alterna-
tives, and only in application to aromatic acids. For aliphatic
hydroxamic acids such data are absent. It has also been well estab-
lished that tautomerisation of hydroxamic acids to the enol form -
RC(OH)@N(OH) does not occur to any appreciable extent (Hadzi
and Prevoesek, 1957).
Complexes of hydroxamic acids of differing stabilities with
metal ions such as Nb, Ti, Mn, V, Zr, Hf, Ta, Fe, Cu, Co, Sn, Al, rare
earths have been reported (Brandt, 1960). Rather strong complexes
are formed with the highly charged rare-earth elements and alumi-
num; the strongest complexes are formed with Fe+3 and probably
with Ta+5 and Nb+5. Weakest complexes are with alkaline earth
metal cations like Ca+2 and Ba+2 (Pradip, 1987; Bogdanov et al.,
1977). Since there is a definite evidence for the existence of intra-
molecular hydrogen bonding in hydroxamic acids, as given in
Fig. 6a, the structure given in Fig. 6b has been considered to be very
reasonable for their metal complexes (Raghavan and Fuerstenau,
1975). However, studies by Russians (Shenderovich et al., 1979)
on the influence of structural characteristics of hydroxamic acids
on their dissociation and complex formation indicates that aro-
Fig. 6. (a) Intramolecular hydrogen bonding in alkyl hydroxamic acids and (b)
mode of complexation of alkyl hydroxamate anion with metal ion.
 S.I. Angadi et al. / Minerals Engineering 70 (2015) 178–200
matic hydroxamic acids have a different character of dissociation
because of the strong inductive effect of the phenyl substituent
on NH group than OH group. Thus in the Nuclear Magnetic Reso-
nance (NMR) spectrum of potassium salt of benzohydroxamic acid
the signal of a proton of NH group is absent while the signal for the
proton of OH is retained, which confirms the presence of species IV
(Fig. 5) in solution.
Structural characterization of tin (IV) complexes of aromatic and
aliphatic hydroxamic acids were studied in detail by several
researchers (Shenderovich et al., 1979; Lyle and Shendrikar, 1966,
1965). A derivative of hydroxamic acid, N-Benzoylphenylhydroxyl-
amine (BPHA), was used to quantitatively precipitate tin, both
stannous and stannic (Ryan and Lutwick, 1953; Lutwick and Ryan,
1954). The infra-red spectra of the precipitated complex
indicated the formation of an inner complex of the composition
Sn(C13H10O2N)2Cl2 and not an addition compound. The spectra also
show that the tin compound appeared to contain hydroxyl
hydrogen of BPHA and tin is combined with carbonyl oxygen, as
given in Fig. 7.
NMR studies by Shenderovich et al. (1979) on the heavy metal
salts of hydroxamic acids formed with aliphatic derivatives indi-
cate the presence of anion of from V (Fig. 5). The analogues nature
of the IR spectra of iron and tin hydroxamates led them
(Shenderovich et al., 1979) to conclude that the most probable
Fig. 7. Structure of tin benzophenylhydroxamic acid complex (Shenderovich et al.,
1979).
Fig. 8. Suggested mode of complexation of alkyl hydroxamate anion to stannic ion
(Shenderovich et al., 1979).
Fig. 9. Structures of alkyl hydroxamate anion in dynamic equilibrium in water medium (Shenderovich et al., 1979).
187
coordination of tin ion was through two oxygen atoms in the
ligand molecule as given in Fig. 8. The possibility of coordination
through nitrogen and oxygen atoms is rejected on the ground that
resulting structure is a four-membered chelate ring, which is not
favored thermodynamically.
The formation of such a complex made them (Shenderovich
et al., 1979) to advocate that the mixture of anions as shown in
Fig. 9 in a solution will be in dynamic equilibrium. They
(Shenderovich et al., 1979) have also reported that the type of com-
plexation given by them is in keeping with the concepts of molec-
ular-orbital theory. The p orbitals of adjacent nitrogen and oxygen
atoms of the hydroxamate grouping form common orbitals, one of
which has greater and other less energy. The p⁄ orbital of higher
energy, which includes a contribution of the atomic orbitals of oxy-
gen, on complex formation overlaps to a greater extent than the
orbital of nitrogen with the vacant orbital of the metal.
Many researchers (Sreenivas and Manohar, 2000; Sreenivas and
Padmanabhan, 2002; Wang et al., 2013) have studied surface
chemistry and flotation characteristics of cassiterite with alkyl
hydroxamic acids/salts. Investigation results show that octyl
hydroxamic acid adsorbs on the cassiterite surface by physical
and specific forces. The maximum adsorption occurs at acidic pH
due to involvement of surfactant and uncharged and/or moder-
ately negatively charged cassiterite. Studies on alkyl hydroxamates
of varying carbon chain lengths (8, 10, 14) show good flotation
with higher carbon chain length collector.
Surface behaviour and flotation of cassiterite with salicylhydr-
oxamic acid were reported by Qin et al., 2011. Experimental results
on <74 lm particles show that the adsorption of salicylhydroxamic
acid on cassiterite was high at neutral pH. The isoelectric point of
cassiterite shifts towards acidic pH in the presence of salicylhydr-
oxamic acid. Investigations on adsorption, electrophoretic mobil-
ity, and IR spectrum indicated that the salicylhydroxamic acid
adsorb on the cassiterite following physical and chemical forces.
6.2.6. Miscellaneous reagents and methods
Use of mixture of collectors to improve the flotation perfor-
mance is increasing day-by-day. It is reported (Bradshaw et al.,
1998) that the synergistic effect of collectors is higher than the
sum of individual reagents. Research articles on this topic are lim-
ited as of now, since, the mechanism of collector interactions in
improving the flotation performance in not clearly known. Mixture
of thiol collectors in the flotation of sulphide minerals has been
studied by McFadzean et al., 2013. These results show that ethly
xanthate and diethyl dithiophosphate mixture of collectors in the
ratio of 10:90 could recover 92.2% galena in contrast to 89%
obtained from either of them at optimised conditions. Clariant
mining solution is reporting mixture of collectors (alkane phos-
phonic acid, alkyl sulpho succinate, and phosphoric acid ester)
for the flotation of cassiterite. These collectors are very selective
and addition of these in different stage improves cassiterite flota-
tion (Clariant Mining Solutions, 2012).
Flotation of cassiterite using cupferron was reported by Vivian
in 1927. Ammonium salt of N-nitrosophenylhydroxyl amine (cup-
ferron) could recover 90% of tin with a concentrate Sn content of
25% from the ore containing 2.5% Sn. Cupferron forms O and O type
metal chelates and the arrangement of the atoms in the molecule
188 S.I. Angadi et al. / Minerals Engineering 70 (2015) 178–200
follows AOA and AN@O. This reagent is considered specific for
Fe(II) and Cu(II), but it forms chelates with several other metals
including Sn(IV) (Nagaraj, 1988).
Polkin et al. (1974) reported the efficacy of di-(2-ethyl) hexyl
phosphoric acid ester (DEHPA) on flotation of fine cassiterite ores
having complex composition [ferruginized quartz (50–60%), tour-
maline (30%) and iron hydroxide (10%)]. The experimental result
shows higher flotation performance at pH 3–3.5. The consumption
of DEHPA at rougher flotation stage was 0.7–0.8 kg/ton. The ratio of
concentration of Sn was 10–18 with 50–65% recovery.
Use of salicylaldehyde in the flotation of cassiterite was
reported by Rinelli et al. (1976) and Marabini (1978). Results show
that the concentrate assaying 1.5% Sn with 88% recovery was
obtained from an ore containing 0.4–0.5% Sn. However, the reagent
consumption was very high (8–10 kg/ton). It was also observed
that the recovery enhanced to 95% with the grade of 2.5% Sn, when
same quantity of salicyaldehyde was added during the grinding
stage.
Doren et al. (1979) studied the influence of non-ionic surfac-
tants on the flotation of cassiterite. The investigation results show
a favourable influence of the combination of sulfosuccinamate-
alkyl polyoxyethylene on selectivity and recovery of tin flotation
at pH 4.5 (isoelectric point of cassiterite).
Kirillova and Yusupov (1990) have studied the influence of
mechanical activation on cassiterite flotation. The studies showed
that mechanical activation was responsible to impart structural
defects on cassiterite with the major changes in tin-oxygen bond
strength and enthalpy of formation of SnO2.
Cheng and Zhu (1986) reported the performance of alkyl phos-
phorous esters on cassiterite flotation. The results of this study
showed that alkyl phosphorous esters are effective collectors when
the alkyl group is octyl, decyl and dodecyl. Flotation studies on a
mixture of – 10 lm cassiterite and quartz (containing 7.1% Sn)
show that it is possible to achieve 89.9% recovery with 48.8% Sn
content. When the experiments repeated with an undeslimed mix-
ture of – 40 lm cassiterite and quartz (head assay of 7.5% Sn), a
product of 73.5% Sn content with 95% recovery was achieved.
Oliverira and Adamian, 1992 have studied selective separation
of cassiterite and fluorite using anionic collectors. The studies were
focused on adsorption, electrophoretic mobility, and suspension
stability measurements of both cassiterite and fluorite. Micro-flota-
tion experiment results showed that at low concentration of anio-
nic collector fluorite can be selectively floated from the cassiterite
particles.
Selective flotation of cassiterite from synthetic mixtures of cas-
siterite-quartz and cassiterite-calcite was attempted by Wu and
Zhu (2006) using benzohydroxamic acid. Micro-flotation studies
show that benzohydroxamic acid floats cassiterite particles effi-
ciently than calcite and quartz. The interaction of cassiterite and
benzohydroxamic acid have been analysed through zeta potential
measurements and infrared spectra studies, which confirms the
collector adsorption on the mineral surface following chemisorp-
tion with the formation of Sn-benzohydroxamic acid.
Choi et al., 1998; Zeng et al., 2000 have studied the influence of
metal cations such as lead, ferric, ferrous, aluminium, manganese,
calcium on flotation of cassiterite, wherein sulphosuccinamate was
used as a collector. The micro-flotation tests followed by X-ray
photoelectron spectroscopy (XPS) analysis with and without metal
cations show that the lead ions activate the cassiterite surface
whereas other cations depress the mineral surface.
Bulatovic and De Silvio (2000) have developed the process for
the removal of zircon, tantalum and columbite impurities from
tin gravity concentrate following direct flotation of tin using a mix-
ture of sulphosuccinate collector modified with fatty alcohol ester
sulphate and depression of impurities using organic acids and
sodium silicate. Experimental results show that it is possible to
upgrade SnO2 content to 90% in the concentrate from the feed
containing 58% with 90% removal of impurities.
Arslan et al., 2002 developed a processing flowsheet for the
recovery of Cu and Sn from the copper refining slag collected from
Sarkuysan A.S. that contain about 22% Cu and 2.3% Sn. The
flowsheet includes comminution, classification, flotation and
leaching stages to recover Cu and Sn values.
Ibezim-Ezeani and Anusiem, 2011 studied the thermodynamics
of adsorption of palmitate and laurate soaps onto galena, hematite
and cassiterite surfaces, wherein, different isotherm models were
used to evaluate the adsorption capacities. The Langmuir isotherm
model gave best fit to the experimental data with monolayer
adsorption capacity values following the order galena > hema-
tite > cassiterite for both (palmitate and laurate) soaps. Computa-
tion of Gibbs free energy (DG), enthalpy (DH) and entropy (DS)
indicated that the adsorption process is spontaneous, exothermic
and is predominantly physisorption.
Liu et al., 2011 have developed beneficiation flowsheet for a
fine-sized cassiterite bearing magnetite ore collected from Sichuan
province, China containing 0.39% Sn and 23.20% Fe. The character-
isation studies indicated that 90% cassiterite values found liberated
at – 0.01 mm size. Beneficiation flowsheet incorporating commi-
nution, magnetic separation (two stage), and shaking table could
separate iron concentrate (assays 61.69% Fe with recovery of
75.09%), tin concentrate (assays 27.21% Sn with 56.97% recovery),
and sulphur concentrate (assays 40.86% S with recovery values of
32.03%).
Qin et al., 2012 studied electro-flotation of cassiterite fines,
wherein, particle bubble collision and its attachment were calcu-
lated following relevant equations available in the literature.
Gonzales et al., 2013 have studied electro-flotation of cassiterite
fines using a bioreagent Rhodococcus opacus (R. Opacus). Surface
characterisation studies such as zeta potential, contact angle, and
adsorption measurements reveal the interaction between Rhodo-
coccus opacus and the cassiterite mineral. The interaction of bior-
eagent on cassiterite fines increases the contact angle. Electro-
flotation results show that the bioreagent could recover about
65% cassiterite values at pH 5, concentration 2.87  1012 cells/ml
(50 mg/L) and current density of 51.4 mA/cm2.
6.3. Effect of particle size on tin flotation
Trahar (1981) identified the role of particle size in flotation fol-
lowing the data obtained from the plant survey and related labora-
tory batch tests. It has been realised from the data that the degree
of hydrophobicity is a function of particle size; hence recovery-size
curves play a valuable diagnostic tool in assessing the flotation per-
formance. The recovery-size curve shown in Fig. 10 gave in-depth
information about the particle size effects in flotation, wherein,
recovery of particular size fraction has been plotted against the
average size. The plot has characteristic curve divided into three
regions; fines, intermediate, and coarse. Intermediate size fraction
is favourable to flotation compared to fines and coarse particles.
The shape of the curve remains similar for flotation of all types
of minerals; however, demarcation of these three regions would
vary based on the physical and mineralogical characteristics of
the feed material.
Fig. 11 shows the batch flotation results on the feed sample col-
lected from the Renison tin concentrator. These experiments were
carried out by using p-tolyl arsonic acid (pTA) as a collector
(0.5 kg per tonne) at pH 5.5, these conditions are mostly influencing
the recovery of gangue minerals (siderite, tourmaline and other sil-
icates) to the concentrate through entrainment (Goodman and
Trahar, 1977). The recovery of gangue (siderite) follows a similar
trend in the plant data. Further, it has been analysed that pTA is a
weak collector for cassiterite. The required rate of flotation was
 S.I. Angadi et al. / Minerals Engineering 70 (2015) 178–200
Fig. 10. Influence of particle size in cassiterite flotation (Trahar, 1981).
Fig. 11. Batch flotation results on cassiterite sample collected from Renison tin
concentrator (Trahar, 1981).
attained in the plant by using higher collector and frother additions,
higher pulp level and aeration rates. On the contrary, such condi-
tions yield high water recovery rates to the concentrate leading to
the entrainment of fine gangue. Particle size analysis indicated that
96% of the feed material is finer than 20 lm and 30% is finer than
5 lm. It is reported that the flotation efficiency was very low for
the cassiterite particles <5 lm. In conclusion, feed containing 2%
Sn has been upgraded to 25% Sn with 85–90% recovery.
6.4. Fine particle processing
Fine particle processing has gained considerable attention of
researchers due to inefficiency of the flotation to treat ultrafine
189
particles (Sivamohan, 1990). Reduction in flotation efficiency is
attributed to the fact that finer particles project smaller mass, lar-
ger surface area, higher solubility in aqueous medium, slime coat-
ing, etc. Some physico-chemical separation techniques that are
used to concentrate fine cassiterite particles (10 lm) are pre-
sented hereunder.
Attia et al. (1987) studied poly methyl vinyl oxime and other
polyoximes for the selective flocculation of cassiterite from tour-
maline and quartz. Flocculation tests were conducted on synthetic
mixture and also on a tailing sample from Catavi. The studies indi-
cated that the poly methyl vinyl ketone oxime (PMVOX) and poly-
acrylamide formaldehyde oxime (PMFOX) are selectively
flocculating cassiterite. It has been observed from the experimental
data that PMFOX (molecular weight 105) with 100 ppm concentra-
tion could flocculate 90% cassiterite particles, yielding 10% Sn in
the flocculated fraction with poor recovery values (4.4%). The
design of a selective polymeric flocculant for cassiterite was
attempted by Clauss and coworkers (1976). They modified poly-
acrylamide flocculant with 8% hydroxamic acids, 69% amide and
23% carboxyl groups. The modified polymer selectively flocculates
the cassiterite from the mixture of quartz in the pH range 3.5–7. By
adding 0.4 gm/l of the modified polymer to a mixed suspension of
30% cassiterite and 70% quartz, the cassiterite was upgraded to 92%
in the flocs, with 65% recovery.
Zambrana et al. (1974) have shown the ability of liquid–liquid
extraction technique to recover – 10 lm cassiterite particles using
low molecular weight petroleum derivatives and Aerosol 22 (a
commercial sulfosuccinamate) collectors. The results indicated
that it is possible to upgrade 9% Sn with 78% recovery following
rougher and cleaner stages, wherein the tin enrichment ratio of 6
and 9.4 obtained in respective stages.
Warren (1982) reported the flocculation of stirred suspension of
cassiterite and tourmaline. He observed that styrene phosphonic
acid and benzyl arsonic acid can float cassiterite but does not
induce shear flocculation. Long chain surfactants such as sodium
oleate or a sulfosuccinamate were more successful. The efficacy
of sulfosuccinamate in shear flocculation of cassiterite was studied
by Bilgen et al. (1994). Hogan et al. (1979) studied electro-flotation
of cassiterite using sulfosuccinamate as a collector.
The application of spherical agglomeration and the use of cat-
ionic reagents such as laury amine acetate for the flotation of cas-
siterite were studied by Farnand et al., 1964. Collins et al. (1968)
reported that few researchers attempted to sulphidize the cassiter-
ite surface and then float the mineral with long chain xanthates.
6.5. Recovery from tailings
Tin recovery from old tailing dumps is gaining wide importance
due to increased metal price in the market. Many old workings
located in Australia, Bolivia, Peru and South Africa are set to rein-
state tin recovery operations. Table 7 shows estimated reserves
with metal contents in few old tailing damps. Advanced gravity
concentration, flotation, and fuming techniques are employed to
recover tin values present in the tailings.
Pilot-scale investigations carried out on Kenko and Catavi tail-
ings indicated that it is possible to up-grade 54–56% Sn from the
feed content 0.2–0.4% Sn with significant recovery values. Investi-
gations on Peru’s San Rafael tailings indicated that the tailing
recovery project could compensate the present production losses.
Zaaiplaats tin tailing dumps in South Africa are estimated to
contain 2600 to 4500 tonnes of tin. Tin values dumped in Zaaipla-
ats tailing pond due to the limitations of old processing flowsheet
that consists of stamp-mills and gravity concentrators (shaking
table and spiral). Recent studies on pilot-scale Falcon UF concen-
trator followed by shaking table indicated that it is possible to
recover fine cassiterite values from the tailings.
190 S.I. Angadi et al. / Minerals Engineering 70 (2015) 178–200
Table 7
Tin tailing projects with estimated reserves and quantity (as on July 2014).
Tailing projects Reserves (million tonnes)
Renison, Australia 19.2
Cleveland, Australia 3.8
Kenko, Bolivia 9.0–9.3
Catavi, Bolivia 19–20
San Rafael, Peru 7.6
Zaaiplaats, South Africa 2.6–3.2
Recovery of tin values from the gravity tails containing 0.24% Sn
collected from Tosham, Haryana, India was attempted by Sreenivas
and Manohar (1998, 1999). Large-scale flotation experiments were
carried out on the gravity tailing sample using phosphonic acid,
sulfosuccinamate and phosphoric acid ester collectors. Experimen-
tal results show that it is possible to achieve a product grade of 7%
Sn with recovery of about 55% from the reagent combination;
phosphoric acid ester – sodium silicofluoride – sulphuric acid
and citric acid.
Zhou et al. (2014) studied the beneficiation of cassiterite tailing
slimes from Datun concentration plant following flotation with
benzohydroxamic acid as a collector, lead nitrate as an activator,
and pine oil as a frother. The cassiterite occurrence in the tailings
is fine grained and associated with mainly iron and calcium bear-
ing minerals. In the proposed method desliming and use of disper-
sant and depressant are evaded due to unwanted tin losses in the
flotation tailings. The collector, activator, and frother combination
could enrich the Sn values to 3.5% from the feed containing 0.18%
Sn with recovery values of 74–75%.
Tin in low-grade ores is generally associated with iron, silica,
and alumina bearing gangue minerals. Cassiterite present in such
a type of ores is in the form of fine to ultra-fine inclusions within
the gangue phase; as a result, it is difficult to recover fine tin values
following gravity and flotation techniques. Usually, fuming is prac-
ticed to recover fine tin from the low-grade ores, which facilitates
release of cassiterite from the gangue mineral cluster following the
reactions:
Cassiterite reduction to stannous oxide
C þ CO2 ! 2CO
SnO2 þ CO ! SnO þ CO2
Stannous oxide reaction with sulphide
SnO þ FeS ! FeO þ SnS
Stannous sulphide is driven off as a vapour at 1250 °C and
passed through freeboard of the kiln. Oxygen is introduced into
the kiln. Stannous sulphide is oxidised back to stannic oxide
(SnO2), which is in the form of a fume. Later, SnO2 is collected after
gas cooling in the kiln by means of a baghouse fabric filter.
SnS þ 2O2 ! SnO2 þ SO2
The sulphur dioxide removed from the gas stream using a lime
scrubber, wherein, calcium sulphate is formed for the safe disposal.
SO2 þ CaO ! CaSO3
CaSO3 þ O2 ! 2CaSO4
7. Beneficiation flowsheets and plant practices
The tin processing flowsheets are somewhat complex as it
involves controlled comminution, and multi-stage concentration
for coarse, fine, and ultra-fine particles. Most of the tin produced
Assay (%) Webpage references
0.45% Sn and 0.21% Cu Metals X, Ltd. (2014)
0.30% Sn and 0.13% Cu Elemento,s Ltd. (2014)
0.38–0.40% Sn Victory Mines (2014)
0.29–0.31% Sn ITRI (2014a)
1.00% Sn ITRI (2014b)
0.08–0.197% Sn Bushveld Minerals Ltd. (2014)
during 1950s and 1960s from the alluvial deposits were using
washing, sizing, and gravity concentration (jigs, sluices, tables)
techniques. The concentrate produced after a number of roughing,
scavenging and cleaning stages would assay marketable grade con-
centrate with relatively low recovery of tin values. This is attrib-
uted due to fine cassiterite loss (0.4–0.8%) in the gravity tailings
(Bulatovic, 2010).
Tin content in the hard-rock deposits assays 0.4–1.5% and even
richer in some occurrences (Bulatovic, 2010). Most of the rich
deposits are exhausted and currently very low-grade ores are pro-
cessed. Low-grade ores are fine grained and tin values are highly
disseminated in the ore body. Beneficiation of such ores creates a
number of problems including fine tin losses in the tailing stream.
Typical recovery values from the low-grade ores would not exceed
50–60% Sn by gravity units, hence a combination of gravity and flo-
tation techniques are employed to improve the recovery values to
more than 70%. In many instances, gravity concentrate contains
sulfides that can be removed by the flotation cells to generate
the final concentrate. During 1970s and 1980s majority of the tin
beneficiation plants have introduced flotation circuit to recover
fine tin from the gravity tailings (Turner and Hallewell, 1993;
Bulatovic, 2010). Tin beneficiation flowsheets are discussed here-
under with the salient features of the processes incorporated and
changes made with the advent of new technology in attaining
higher concentrate grade and recovery.
7.1. Renison, Australia
Cassiterite in Renison Bell mine is mainly associated with pyr-
rhotite, quartz, dolomite, siderite, and dorite. Beniuk et al. (1994)
discussed the process improvements in the gravity concentration
circuit. In addition, the research paper highlights beneficiation
practice and first installation of the Kelsey centrifugal jig. Fig. 12
shows the gravity concentration flowsheet at Renison concentra-
tor, Australia (Beniuk et al., 1994). The requirement of incorporat-
ing Kelsey jig in the plant was to improve the plant efficiency and
operating economics as well as to reduce the environmental pollu-
tion by closing the acid leaching plant. It is reported that the Kelsey
jig was able to handle particle size 40 + 5 lm. The finer particle
separation was possible due to the centrifugal force applied in
addition to the gravitational force. The gravity circuit produces
plant’s majority of the tin concentrate. The Kelsey jig design limi-
tations and subsequent important modifications in the plant envi-
ronment are summarized in this article.
The plant performance after installing J650 model Kelsey jig in
the gravity concentrate and tailing streams are presented in
Table 8.
This article provides an overview of the plant commissioning of
J650 model Kelsey jig along with its’ operational difficulties and
subsequent modifications in screen aperture, mechanical arrange-
ments, etc., that led to the development of a new industrial jig. The
studies show that the performance of Kelsey centrifugal jig was
better than conventional shaking tables in terms of product grade
and recovery.
 S.I. Angadi et al. / Minerals Engineering 70 (2015) 178–200 191

Fig. 12. Tin gravity recovery circuit at Renison Ltd., Australia (Beniuk et al., 1994).

Table 8
Plant data on J650 model Kelsey jig treating gravity concentrate and tailings (data presented in average values).

Sample Feed rate (t/h) Feed Sn (%) Concentrate Sn (%) Recovery of Sn (%)
Gravity concentrate 2.1 24.28 63.83 65.05
Gravity tailing 2.2 0.69 4.00 45.53

Bulatovic (2010) summarized flotation operation at Renison
concentrator. The gravity concentration plant was recovering 45–
50% tin. Later, flotation circuit was developed and incorporated
along with the gravity circuit to enhance the tin recovery values.
Fig. 13 shows flotation circuit consisting of desliming units fol-
lowed by sulfide and tin flotation units. Each of the sulfide and
tin flotation banks consists of rougher, scavenger and cleaner units.
Primarily, sulfides are removed from the gravity tailings using cop-
per sulfate as a depressant, xanthate as a collector, and cresylic
acid as a frother at pH 6 following rougher and two stages of clean-
ing. The non-froth product from the sulfide flotation banks was
further subjected to tin recovery cells arranged in the order of
rougher, scavenger followed by four stages of cleaning. The
detailed reagent scheme operated at Renison is presented in
Table 9. Initially, arsonic acid was used as a tin collector, subse-
quently replaced with styrene phosphonic acid and later sulpho-
succinamate (CA 540, Allied Chemicals). The metallurgical results
obtained during 1982 are shown in Table 10.

7.2. Wheal Jane, UK

Turner and Hallewell (1993) described in detail the Wheal Jane

tin beneficiation plant flowsheet and process developments under-
taken while improving the product grade and recovery. Wheal Jane
Fig. 13. Flotation circuit to recover tin from gravity tailings at Renison (Bulatovic, plant was treating about 180,000 tonnes per annum of cassiterite
2010). ore and was producing 57–60% Sn in the concentrate with 82%
192 S.I. Angadi et al. / Minerals Engineering 70 (2015) 178–200

Table 9
Operating reagent scheme of flotation circuit at Renison.

Reagent Sulphide circuit Tin circuit

Depressants Copper sulphate (CuSO4) 200–300 g/t Sodium silicate (Na2SiO3) 800–1500 g/t and Sodium fluoride (NaF) 400–600 g/t
Modifiers Sulphuric acid (pH – 6.0) Sulphuric acid (pH 4.5–5.0)
Collectors Xanthate (50–70 g/t) p-Tolyl arsonic acid (PTTA) emulsified with NaOH (400–700 g/t)
Frother Cresylic acid (20–30 g/t)

Table 10 flotation units during 1993. About 60% of the bulk concentrate was
Performance of Renison beneficiation circuit during 1982. recovered in gravity units assaying 58% Sn and S together. The
Product Weight (%) Assays (% Sn) Distribution (% Sn)
gravity tails deslimed using hydrocyclones to remove 6 lm parti-
cles and coarse stream was further subjected to sulfide scavenger
Gravity concentrate 1.7 41.6 58.3
Tin flotation concentrate 0.7 23.5 13.8
cells. The sulfide minerals floated using a sodium ethyl xanthate
HMS float 23.2 0.17 3.1 as a collector, MIBC as a frother at acidic pH maintained with sul-
Sulphide concentrate 45 0.4 14.5 furic acid. The non-sulfide stream from the scavenger cells fed to
Table tailing 6.8 0.48 2.7 the tin flotation cells.
Tn flotation tailing 17 0.3 4
Several improvements were made in the tin flotation circuit
Slimes 5.6 0.75 3.6
Feed 100 1.24 100 during the period 1980–1993 (Turner and Hallewell, 1993). Ini-
tially, flotation circuit was generating 5% Sn with 40% recovery val-
ues. Over time, many modifications in the circuit were made such
as increasing the flotation residence time, staged addition of collec-
tin recovery from the feed containing about 1.5% Sn. The tin bene- tor and modifying the circuit configuration, to yield higher concen-
ficiation flowsheet shown in Fig. 14 consists of mainly gravity and trate grade 11–12% and recovery 70–80%.

Fig. 14. Cassiterite beneficiation flowsheet at Weal Jane, UK (Turner and Hallewell, 1993).
 S.I. Angadi et al. / Minerals Engineering 70 (2015) 178–200 193

The need for further improvement of the concentrate grade
arose due to collapse in tin price during October 1985. Following
attempts were made to improve the concentrate grade
– Increasing conditioning time of rougher concentrates.
– Reducing entrainment of low-grade slimes by increasing the
froth depth.
– Introduction of flotation column (0.76 m diameter, 9.75 m
long).
– Replacing the process water by fresh water in column and clea-
ner cells, etc.
Consequently the concentrate grade has improved to 50.70% Sn
with 63.31% stage recovery.
Further, laboratory investigations carried out at Camborne
School of Mines revealed that the grade/recovery benefits can be
achieved by incorporating multi-gravity separator in place of flota-
tion column. The influence of operating variables such as feed pulp
density, drum speed, throughput, wash water rate, angle of tilt and
shaking intensity on the performance of MGS was discussed in
detail. Summary of plant test results of mine scale MGS is shown
in Table 11.
The table clearly reveals the improvement in grade and recov-
ery by MGS over a flotation column. The economic gains are related
with the cheaper operating costs of MGS over the flotation column.
Detailed investigations on higher performance of MGS over the flo-
tation column are presented through Tables 12 and 13.
Size analysis and size-wise Sn distribution of concentrate and
tailing samples collected from the flotation column and multi-
gravity separator units are presented in the above tables. The tin
content is mostly distributed in coarse particle size range
(45 + 12 lm), recovery of each size fraction to the concentrate
Table 11
Comparison of flotation column and MGS performance (Turner and Hallewell, 1993).
Sn (%) Flotation circuit recovery of Sn (%)
Feed Tail Concentrate
MGS 0.600 0.209 55.42 65.41
Column 0.575 0.227 50.16 60.79
reveals that the multi-gravity separator could recover most of
the tin values located in 45 + 12 lm size fraction. Whereas, flota-
tion column fails to recover particles in that class as a result recov-
ery of tin was low.
7.3. Rooiberg and Union Tin Mine, South Africa
Falcon (1985) compiled history of tin, occurrence, operations,
processing flowsheets and their developments took place in the
South African continent. Tin in South Africa mainly occurs in
hard-rock deposits of Rooiberg, Union Tin and Zaaiplaats regions
with operating underground mines. Brief tin mining activities in
many mines of these regions are covered in the article. Typical
tin beneficiation flowsheet operated at Rooiberg tin mine is shown
in Fig. 15. The other mines are having more or less similar benefi-
ciation schemes with few variations as per the nature of the raw
material. The Cornish engineers were initially designed and oper-
ated Rooiberg mine. The plant was having a capacity to treat
20,000 tonnes of ore per month with the tin content varying
between 0.5% and 0.7%. The run of mine was crushed, screened
and fed coarse product (12 + 1 mm) to a 310 mm Dynawhirlpool
gravity separator, wherein, separating density of 2.9 was main-
tained using 100 D ferrosilicon medium. The fines fraction was
subjected to a 125 mm DSM (Dutch State Mines) cyclone, which
was operated with 100 D ferrosilicon and magnetite mixture. The
concentrates from the heavy medium separators contain 2–3%
tin was further processed through milling and tabling circuit to
upgrade the tin values to 12–20%. The milling and tabling circuit
consists of stage grinding by rod and ball mills with intermediate
gravity recovery tables. The pre-concentrate was further subjected
to dressing section, which was similar to mill-table circuit in addi-
tion to the flotation cells to remove sulfides. The final concentrate
achieved from this stage assays 60–62% Sn.
Rooiberg tin beneficiation flowsheet was consist of mainly grav-
ity units, hence a lot of fine tin (43 lm) was rejected into the tail-
ings. The Union Tin Mines commissioned South Africa’s first
cassiterite flotation circuit during 1971 and tested many reagents
to recover the tin oxide mineral. The most promising reagents
investigated were iso-hexyl phosphonic acid with sodium oleate,
dialkyl sulphosuccinamate, ethyl phenyl phosphonic acid (EPPA),
and p-tolyl arsonic acid (PTAA). The flotation performance
obtained using these reagents are presented in Table 14. The plant

Table 12
Performance of MGS (Turner and Hallewell, 1993).

Size in microns Concentrate Tailing Feed (calculated) Distribution of Sn. (%) Wt. % recovery to conc. Recovery of Sn to conc. (%)
(Wt. %) (Sn %) (Wt. %) (Sn %) (Wt. %) (Sn %)
+45 3.96 30.88 48.25 0.19 47.90 0.21 14.0 3 9.49
12 60.02 63.77 24.20 0.33 24.48 1.54 52.4 47 79.03
6 30.88 58.36 16.95 0.18 17.06 1.00 23.7 24 82.28
6 5.14 29.58 10.61 0.57 10.57 0.68 9.9 4 16.50
100.00 59.04 100.00 0.26 100.00 0.72 100.0 78 63.87

Table 13
Performance of flotation column (Turner and Hallewell, 1993).

Size in microns Concentrate Tailing Feed (calculated) Distribution of Sn. (%) Wt. % recovery to conc. Recovery of Sn to conc. (%)
(Wt. %) (Sn %) (Wt. %) (Sn %) (Wt. %) (Sn %)
+45 2.98 41.05 49.02 0.15 48.72 0.17 16.8 2 9.72
12 39.10 61.24 21.10 0.20 21.22 0.92 59.6 25 78.60
6 35.74 43.17 18.64 0.16 18.75 0.69 26.2 23 77.00
6 22.19 18.62 11.23 0.53 11.30 0.76 17.4 14 30.99
100.00 44.73 100.00 0.21 100.00 0.49 100.00 64.0 58.53
194 S.I. Angadi et al. / Minerals Engineering 70 (2015) 178–200

Fig. 15. Tin beneficiation flowsheet at Rooiberg, South Africa (Falcon, 1985).

Table 14
Performance of cassiterite collectors at Union Tin Mines (Bulatovic, 2010).

Collector Dosage, g/t pH Sn (%) Distribution of Sn (%)

Iso-hexyl phosphonic acid with 100 5 11 72
Sodium oleate 250
p-Tolyl arsonic acid 350 4.5–5 25 80
Ethyl phenyl phosphonic acid 330 4.5–5 25 62
Dialkyl sulphosuccinamate 400 2.5 10 70

ated at fines (12 lm). The concentration circuit shown in Fig. 16

Table 15
Flotation plant performance at Union and Rooiberg plants treating old tailings
consists of combination of jig, spiral, table and sulfide flotation
(Bulatovic, 2010). cells, which recovers 65% tin values from the feed containing
1.2–1.3% Sn.
Product Weight (%) Sn (%) Distribution of Sn (%)
Feasibility studies carried out on gravity tails showed the possi-
Tin cleaner concentrate 1.5 19.60 61.6 bility of recovering additional 22% tin by flotation technique, with
Sulphide concentrate 2.0 0.68 3.3
this, overall plant recovery increased to 87%. Flotation studies were
Tin flotation tailing 83.2 0.12 21.3
Slimes 13.0 0.40 13.8 carried out with PL520 collector, which is a mixture of dialkyl sul-
Feed 100.0 0.49 100.0 phosuccinamate (R845), phosphoric acid easter (SM15) and fatty
alcohol ester sulfate in the ratio 60:20:20.

7.5. San Rafael, Minsur, Peru

tailing was deslimed at 6 lm and subjected to the flotation circuit
along with PTAA, sodium silicate (dispersant), and sodium fluoride
(depressant), wherein slurry pH of 4.5 was maintained. Flotation
circuit was designed at Rooiberg in 1972, following previous expe-
rience at Union Tin mine to treat current tailings and slimes
reclaimed from the tailing dams. The flotation plant performance
at Union and Rooiberg plants on old tailings are presented in
Table 15.
7.4. Huanuni concentrator, Bolivia
Cassiterite is the main tin mineral along with minor quantities
of stannite in Huanuni deposit, Bolivia (Bulatovic, 2010). The gan-
gue minerals present in the ore are quartz, pyrite, marcasite, pyr-
rhotite, and arsenopyrite. Most of the tin is liberated in the
coarse size fraction (400–300 microns), and some portion is liber-
San Rafael plant was treating the ore assaying 2–5% Sn. The ore
was coarse grained and part of the concentrate was produced in
coarse size (8 mm). Cassiterite is the tin bearing mineral in the
ore, which is associated with silicates, pyrites, pyrrhotite, tourma-
line, copper and silver in small quantities. The gravity concentra-
tion circuit mainly consists of jigs, spirals and tables that
upgrade the tin content to 54% with 80% recovery of tin. Further,
the gravity tails assaying 1.3% Sn was treated in the flotation circuit
(Fig. 17). It consists of desliming cyclones followed by sulfide and
tin flotation cells. The final tin concentrate after three stages of
cleaning enrich SnO2 content to 36%, later, it is subjected to the
multi-gravity separator for further enrichment. The operating con-
ditions of the flotation plant are presented in Table 16.
Ruiz et al. (2004) presented improvements in the grade and
recovery after installation of a pilot-scale jig (GEKKO IPJ 2400) in
 S.I. Angadi et al. / Minerals Engineering 70 (2015) 178–200 195

Fig. 16. Gravity concentration circuit at Huanuni concentrator, Bolivia (Bulatovic, 2010).

the existing plant. The IPJ 2400 jigs were installed with the aim to
recover cassiterite values in the coarse size. The coarse liberated
cassiterite particles would otherwise report to the ultrafines due
to grinding. The concentrate from IPJ 2400 jigs assays 23.5% Sn,
which was further enriched by screening over 2 mm screen. The
coarse fraction (>2 mm) assays 45–50% Sn and the fines (<2 mm)
assays 12–15% Sn. Each stream independently subjected to the
gravity and flotation circuits to enrich the final concentrate to
63% Sn. The jig circuit treating coarse feed material is shown in
Fig. 18.
Fig. 17. Flotation circuit at San Rafael, Peru.

Table 16
Reagents used in flotation circuit at San Rafael (Bulatovic, 2010).

Reagent Sulphide circuit Tin circuit

Depressants Na2SiO3, 200–300 g/t CuSO4, 250 g/t Sodium silicate (Na2SiO3) 250–400 g/t and Sodium fluoride (Na2SiF6) 200–300 g/t
Modifiers Sulphuric acid (pH – 6.0) Sulphuric acid (pH – 4.5–5.5)
Collectors Amyl Xanthate, 60–80 g/t Dithiophosphate (R3477), 15–20 g/t R 845 (Cytec), 50–100 g/t
196 S.I. Angadi et al. / Minerals Engineering 70 (2015) 178–200
Fig. 18. Coarse cassiterite recovery circuit at San Rafael, Peru (Ruiz et al., 2004).
7.6. Tin-Tungsten multi-mineral ore, Kyrgyzstan, Central Asia
Srinivas et al. (2000) and Sreenivas et al. (2004) reported the
development of a processing scheme for the recovery of tungsten
and tin values from the multi-mineral concentrate of wolframite,
scheelite, and cassiterite collected from Kyrgyzstan (Central Asia).
The primary gravity concentrate collected from the mine site
assays about 18.05% WO3 and 38.11% SnO2. Both tungsten minerals
wolframite and scheelite occurs in liberated state as well as fine
distribution in each other. Cassiterite also found in liberated as
well as intergrowth of columbite/tantalite and has fine dissemina-
tion of tungsten minerals within it. Because of this complex asso-
ciation of minerals an integrated process has been developed,
which consists of physical beneficiation and chemical extraction
techniques. The physical beneficiation route tested is shown in
Fig. 19. The specific gravity, magnetic and electrical conductivity
of wolframite, scheelite and cassiterite were explored in the sepa-
ration. The concentrate thus generated was purified following the
chemical route depicted in Fig. 20. Tungsten extraction was carried
out by a soda ash roast-aqueous leaching method. This method
recovers about 90% tungsten values and 8–10% loss in residue.
The residue contains 40% SnO2 values that will be mixed with
the cassiterite gravity concentrate to improve overall recovery val-
ues. The combined concentrate assays 67% SnO2 that was further
processed either by smelting-refining route or roasting-smelting-
refining route. The proposed integrated flowsheet would recover
80–90% tungsten and tin values.
7.7. Uljin deposit, South Korea
Tin occurs in Uljin mine in a hard-rock deposit along with peg-
matite host rocks (Moon et al., 1996). The feed sample analyse 6.4%
Sn, 59.0% SiO2, 13.4% Al2O3, 5.2% Fe2O3 contents. Characterisation
studies revealed that the tin bearing mineral in the ore is cassiter-
ite, which occurs in association with quartz, albite, biotite, horn-
blend, and chlorites. Experiments were carried out on various
gravity concentrators and flotation cells to upgrade the Sn values.
Coarse fraction was processed through mineral jig, spiral concen-
trator and shaking table, whereas, fines fraction was processed
using shaking table and flotation cells. Investigation results show
that the coarse circuit (+0.71 mm) could enrich Sn content to 50%
with 53–54% recovery values (Jeon et al., 2011, 2012). The fines cir-
cuit consists of shaking tables, ball mill and flotation cells to treat
0.71 mm fines and coarse circuit tails. The fines circuit could
enrich Sn content to 47% with additional 39% tin recovery
(Angadi, 2012; Jeon et al., 2013). Hence developed flowsheet
shown in Fig. 21 enriches the tin content in the final concentrate
to 48–49% with overall recovery of about 92%.
8. Conclusions
The beneficiation of cassiterite is an age-old technique that has
undergone many changes over time. The commercial demand for
tin fluctuates with respect to its area of applications. During the
1950s, demand for metal was mainly from the tin plate industries,
while in recent times more demand is reported from the electronic
and soldering industries. Cassiterite is the prime economic tin min-
eral that occurs in alluvial and hard-rock deposits. The existing lit-
erature on cassiterite beneficiation is mainly focused on gravity
concentration and flotation techniques. In addition, a few pub-
lished articles discuss the ultra-fine particle processing techniques
such as selective flocculation, shear flocculation and spherical
agglomeration.
Many gravity concentrators have been used in the cassiterite
beneficiation to treat coarse (jigs, heavy medium baths/cyclones),
intermediate (spirals and shaking tables), and fine (advanced grav-
ity concentrators) particles. Processing of cassiterite fines was one
of the driving forces for the development of advanced gravity sep-
arators. The efficacy of advanced gravity concentrators such as the
Kelsey jig, Bartles Mozley separator and Mozley multi-gravity sep-
arator for treating ultrafine particles has been tested in the pilot-
plant and plant environments.
A considerable number of research articles have been published
about new surfactants, their chemical aspects, surfactant func-
tional groups, complex formation with the cassiterite surface, etc.
The widely reported surfactants in cassiterite flotation are cupfer-
ron, arsonic acid, phosphonic acid, fatty acids, salicyaldehyde, sulfo
succinamate, hydroxamic acids, etc. Most of these surfactants
adsorb on the cassiterite mineral by physisorption and some with
other specific forces. Many of these collectors are efficient to
recover particle size –38 + 6 lm. The flotation efficiency decreases
for >38 lm and <6 lm particle sizes. Unfortunately, several plants
are losing cassiterite values in the ultrafine sizes. This requires a
great deal of future study in order to develop tailor-made surfac-
tants to float ultrafine particles.
Development of advanced gravity concentrators and suitable
surfactants to recover tin values from ultrafine particle size is the
subject of considerable interest. For sustainable utilization of nat-
ural resources and to meet the growing demand it is essential to
 S.I. Angadi et al. / Minerals Engineering 70 (2015) 178–200 197

Fig. 19. Physical beneficiation flowsheet for Tin-Tungsten multi-mineral ore, Kyrgyzstan, Central Asia.

Fig. 20. Separation of tungsten and tin values from wolframite–scheelite–cassiterite containing concentrate.
198 S.I. Angadi et al. / Minerals Engineering 70 (2015) 178–200
Fig. 21. Beneficiation flowsheet for tin ore collected from Uljin deposit, South Korea.
develop a technology to recover tin values from the low-grade ores
and ultrafine tailings.
Acknowledgements
The first author would like to acknowledge the Indo-US Science
and Technology Forum (IUSSTF) for granting Indo-US Research Fel-
lowship 2013. The authors also wish to thank Ms. Dorrie Spurlock
for proofreading the manuscript.
References
Abeidu, A.M., 1974. Comparative studies on the flotation of wolframite. J. Mines
Metals Fuels 22, 107.
Abeidu, A.M., 1975. Flotation studies on wolframite. Trains. Min. Met. 84, C5.
Agarwal, Y.K., 1979. Hydroxamic acids and their metal complexes. Russ. Chem. Rev.
48 (10), 948–963.
Andrews, P.R.A., 1991, Differences in collector selectivity between cassiterite and
two commonly occurring silicate minerals, topaz and tourmaline. In: 17th
International Mineral Processing Congress, Dresden, Pre-print volume IV,
pp. 1–11.
Angadi, S.I., 2012, Development of process flowsheet for tin ore collected from Uljin
deposit, South Korea. Internal Report submitted to Korea Institute of
Geosciences and Mineral Resources (KIGAM), South Korea.
Arbiter, N., 1968, Beneficiation of Cassiterite Ores by Froth Flotation, British Patent
No. 110643.
Arbiter, N., 1977. Flotation of tin ores: A review. International Tin symposium, La
Pez, Bolivia.
Arslan, F., Giray, K., Önal, G., Gürkan, V., 2002. Development of a flowsheet for
recovering copper and tin from copper refining slags. Europ. J. Min. Process.
Environ. Protect. 2 (2), 94–102 (1303-0868).
Attia, Y.A., Fuerstenau, D.W., 1978. Principles of separation of ore minerals by
selective flocculation. In: Li, N., Stern, S., Long, R., Somasundaran, P. (Eds.),
Recent Developments in Separation Science, vol. IV. CRC Press, West Palm
Beach, Florida, pp. 51–79.
Attia, Y.A., Sinclair, R.G., Markle, R.A., Cousin, M., Krishnan, S.V., Keys, R.O., 1987.
Preparation of poly (methyl vinyl oxime) and other polyoximes for the selective
flocculation of cassiterite from tourmaline and quartz. In: Attia, Y.A. (Ed.),
Flocculation in Bio-Technology and Separation System. Elsevier, Amsterdam,
pp. 263–275.
Baldauf, H., Schoenherr, J., Schubert, H., 1985. Alkane dicarboxylic acids and
aminonapthal sulfonic acids – a new reagent regime for cassiterite flotation. Int.
J. Min. Process. 15, 117–133.
Bandopadhyay, A., 2000, Multi-gravity separator – an equipment for separation of
fines. In: Bhattacharyya, K., Singh, R., Goswami, N.G., (Eds.), Processing of Fines
(2), India. pp. 81–92, ISBN: 81-87053-53-4.
 S.I. Angadi et al. / Minerals Engineering 70 (2015) 178–200
Barsukov, V.L., Klintsova, A.P., 1970. Solubility of cassiterite in water and aqueous
NaOH at 25 °C. Geochem. Int. 7 (10), 849.
Beniuk, V.G., Vadeikis, C.A., Enraght-Moody, J.N., 1994. Centrifugal Jigging of gravity
concentrate and Tailing at Renison Limited. Miner. Eng. 7 (5/6), 577–589.
Benzaazoua, M., Marion, P., Liouville-Bourgeois, L., Joussemet, R., Houot, R., Franco,
A., Pinto, A., 2002. Int. J. Miner. Process. 66, 163–181.
Benzaazoua, M., Marion, P., Pinto, A., Migeon, H., Wagner, F.E., 2003. Tin and indium
mineralogy within selected samples from the Neves Corvo ore deposit
(Portugal): a multidisciplinary study. Miner. Eng. 16, 1291–1302.
Bilgen, S., Wills, B.A., Akdogan, G., 1994. Shear flocculation of cassiterite with
sulfosuccinamate surfactant. Trans. Inst. Min. Metall. 103, C220–C223.
Blackburn, W.H., Dennen, W.H., 1988. Principles of Mineralogy. Wm. C. Brown
Publisher, Dubuque (lowa), p. 268.
Bogdanov, O.S., Yeropkin, Y.I., Koltunova, T.E., Khobotova, N.P., Shutchukina, N.E.,
1973. Hydroxamic acids as collectors in the flotation of wolframite, cassiterite
and pyrochlore. In: Jones, M.J. (Ed.), Proceedings of 10th International Mineral
Processing Congress. IMM, London, pp. 553–564.
Bogdanov, O.S., Pondnek, A.K., Rjaby, V.I., Janis, N.A., 1977. Reagent chemisorption
on minerals as a process of formation of surface compounds with a co-
ordination bond. In: XII International Mineral Processing Congress, MME/
DNPM. Sao Paulo, Brasil, vol. 2, pp. 280–303.
Bradshaw, D.J., Harris, P.J., O’Connor, C.T., 1998. Synergistic interactions between
reagents in sulphide flotation. J. South Afr. Inst. Min. Metall., 189–194 (July/
August).
Brandt, W.W., 1960. Analytical applications of hydroxamic acids. Rec. Chem. Prog.
21, 159–177.
Bulatovic, Srdjan M., 2010. Handbook of flotation reagents: chemistry. Theory and
Practice, vol. 2 Flotation of Gold, PGM and Oxide Minerals, September 2010.
Elsevier, ISBN 10:0-444-53082-7.
Bulatovic, S., De Silvio, E., 2000. Process development for impurity removal from a
tin gravity concentrate. Miner. Eng. 13 (8–9), 871–879.
Burt, R.O., 1984. Gravity concentration technology. In: Fuerstenau, D.W. (Ed.),
Developments in Mineral Processing, vol. 5. Elsevier, Amsterdam, p. 521
(Chapter 28).
Burt, R.O., 1988. A review of gravity concentration techniques for processing of
fines. Production and processing of fine particles. In: Proceedings of the
International Symposium on the Production and Processing of Fine Particles,
Montreal, August 28–31. A volume in Proceedings of Metallurgical Society of
Canadian Institute of Mining and Metallurgy, 1988. pp. 375–385.
Burt, R.O., 2000. Gravity concentration. Ullmann’s Encyclop. Indust. Chem. 2000.
http://dx.doi.org/10.1002/14356007.b02_21, Published Online: 15 June.
Burt, R.O., Ottley, D.J., 1974. Fine gravity concentration using the Bartles-Mozley
concentrator. Int. J. Miner. Process. 1 (4), 347–366.
Bushveld Minerals Ltd., 2014, Agreement to Acquire the Zaaiplaats Tin Tailings
Dump, <http://www.londonstockexchange.com/exchange/news/market-news/
> (accessed 08.07.14).
Chakrabarti, D.K., Lahiri, N., 1996. Copper and Its Alloys in Ancient India. Mushiram
Manoharlal, New Delhi, ISBN 81-215-0707-3.
Chatterjee, B., 1978. Donor properties of hydroxamic acids. Coord. Chem. Rev. 26,
281–303.
Cheng, Jianguo, Zhu, Jianguang, 1986. A Study of the Collecting Performances and
Adsorption Mechanism of Alkyl Phosphorous Ester on Cassiterite. Nonferrous
Metals, vol. 38, No. 4, November, pp. 37–43 (Chinese Text).
Chin, P.C., Wang, Y.T., Sun, Y.P., 1979. A new slime concentrator the rocking-shaking
vanner. In: Laskowski, J. (Ed.), Proceedings, Developments in Mineral
Processing, V2, Part B, 13th International Mineral Processing Congress,
Warsaw, 1398–1421, 2 ref. June 4–9.
Choi, Woo-Zin, Jeon, Ho-Seok, Zeng, Qinghua, Jiang, Erlong, Wang, Dianzuo, 1998.
Influence of metal cations on cassiterite flotation. Geosystem Eng. 1 (1), 53–57,
May.
Clariant Mining Solutions, 2012. Non-Sulfide Ores, <http://www.oms.clariant.com/
en-us/mining/Documents/Non-SulfideOresSINGLEPAGES.pdf> (accessed
18.07.14).
Clauss, C.R.A., Appleton, E.A., Vink, J., 1976. Selective flocculation of cassiterite: in
mixtures with quartz using a modified polyacryamide flocculant. Int. J. Miner.
Process 3, 27.
Collins, D.N., Kirkup, L., Davey, M.N., Arthur, C., 1968. Flotation of cassiterite:
development of a flotation process. Transact. Inst. Min. Metall. 77, C1–C13.
De Cuyper, J., Salas, A., 1977. Flotation of cassiterite. In: Proceedings of International
Tin Symposium, La Pez, Bolivia.
Doren, A., van Liende, A., van Liende, A., de Cuyper, J.A., 1979. Influence of non-ionic
surfactants on the flotation of cassiterite. In: 13th International of Mineral
Processing Congress. Elsevier, Amsterdam, pp. 86–106.
Earl, B., Ozbal, H., 1996. Early bronze age tin processing at Kestel/Goltepe, Anatolia.
Archaeometry 38 (2), 289–303.
Edwards, G.R., Ewers, W.E., 1951. The adsorption of sodium cetyl sulfate on
cassiterite. Aust. J. Sci. Res. 4 (4), 627–643.
Elementos, 2014. Clevend Tin Project, <http://www.elementos.com.au/
Projects_Cleveland.htm> (accessed 09.07.14).
Emsley, J., 2001. ‘Tin’ In: Nature’s Building Blocks: An A–Z Guide to the Elements.
Oxford University Press, Oxford, England, UK, pp. 445–450, ISBN 0-19-850340-
7.
Exner, O., 1968. Physico–chemical investigations on hydroxamic acids. Dan Tiddsk
Farm 42, 145–169.
Falcon, L.M., 1982. The gravity recovery of cassiterite. J. South Afr. Inst. Min. Metall.,
112–117. April.
199
Falcon, L.M., 1985. Tin in South Africa. J. South Afr. Inst. Min. Metall. 85 (10), 333–
345, October.
Farnand, J.R., Meadus, F.W., Tymchuk, P., Puddington, I.E., 1964. The application of
spherical agglomeration to the fractionation of a tin containing ore. Can. Metall.
Quart. 3 (2), 123–135.
Foo, K.A., Enraght-Moony, J.N.R., Weller, K.R., 1983. Current practices and trends in
the treatment of tin ores of Australia. International Symposium on Resource
Development and Pollution Control, Tsukuba, Japan.
Fuerstenau, D.W., 1984. Pradip, Mineral Flotation with Hydroxamate collectors. In:
Jones, M.J., Oblatt, R. (Eds.), Reagents in the Minerals Industry. Institution of
Mining and Metallurgy, London, pp. 161–168.
Gonzales, Lorgio Gilberto Valdiviezo, Pino, Gabriela Alejandra Huaman, Torem,
Mauricio Leonardo, 2013. Electroflotation of cassiterite fines using a
hydrophobic bacterium strain, REM, R. Esc. Minas, Ouro Preto, 66(4), 507–
512, out.dez.
Goodman, R.H., Trahar, W.J., 1977. Flotation of cassiterite at the Renison tin mine,
Renison Bell, Tasmania. International Tin Symposium, La Paz, Bolivia.
Gorlvoskii, S.I., Eropkin, Y.I., Kursakova, G.M., Koval, E.M., Streltsin, V.G., Khobotova,
N.P. Shtchukina, E.E., 1968. Improvement in concentration technology of some
rare metal ores, based on taking advantage of complexing alkyl hydroxamic
acid peculiarities of action. In: 8th International Mineral Processing Congress,
vol. 1, Leningrad, pp. 398–413 (Russian Text); Paper D3, 9p (English Text).
Gruner, H., Bilsing, U., 1992. Cassiterite flotation using styrene phosphonic acid to
produce high-grade concentrates at high recoveries from finely disseminated
ores – comparison with other collectors and discussion of effective circuit
configurations. Miner. Eng. 5 (3–5), 429–434.
Hadzi, D., Prevoesek, D., 1957. Infra-red absorption bands associated with the
NH group-III Hydroxamic acids and derivatives. Spectrochim. Acta 10 (1),
38–51.
Hogan, P., Kuhn, A.T., Turner, J.F., 1979. Electroflotation studies based on cassiterite
ores. Transact. Inst. Min. Metall. 88, C83–C87.
Holl, C.J., Bromley, A.V., 1988. Application of mineralogy to the beneficiation of a
tin-sulphide ore. Miner. Eng. 1, 19–30.
Houot, R., Desbrosses, Y., 1991. Is the cassiterite contained in complex sulfide
polymetallic ore recoverable? Int. J. Miner. Process. 32, 45–57.
Ibezim-Ezeani, Millicent U., Anusiem, Alphonso C.I., 2011. Thermodynamics of the
adsorption of palmitate and laurate soaps onto some metal ore surfaces in
aqueous media. Afr. J. Pure Appl. Chem. 5 (9), 272–277.
ITRI Tin Explorers, 2014a. Australian Listing for Bolivian Tin Projects, <https://
www.itri.co.uk> (accessed 09.07.14).
ITRI Market Analysis, 2014b. Minsur Commits to Long-term Tin Supply, <https://
www.itri.co.uk> (accessed 09.07.14).
ITRI Briefing, 2011. Historical Trends in Tin Production, <https://www.itri.co.uk>
(accessed 04.02.14).
ITRI Briefing, 2012. Tin Mining and Processing Methods, <https://www.itri.co.uk>
(accessed 04.02.14).
Jeon, H.S., Angadi, S.I., Baek, S.H., 2011, Efficiency evaluation of gravity jigs treating
tin ore. In: XII International Seminar on Mineral Processing Technology, MPT-
2011, October 20–22, NF23.
Jeon, H.S., Angadi, S.I., Baek, S.H., 2012. Selection of gravity concentrators for the
beneficiation of cassiterite ore – a holistic approach. XXVI International Mineral
Processing Congress (IMPC) 2012, New Delhi, 2090–2094.
Jeon, H.S., Baek, S.H., Angadi, S.I., Mishra, B.K., 2013. Optimisation of operating
variables in cassiterite flotation. In: XIII International Seminar on Mineral
Processing Technology, MPT-2013, December 10–12, pp. 183–187.
Khangaonkar, P.R., Kamarudin, H., 1994. Studies on the cassiterite-
sulphosuccinamate flotation system. Int. J. Miner. Process. 42, 99–110.
Kirchberg, H., Wottgen, E., 1964. Investigations Into the Flotation of Cassiterite with
Phosphonic, Arsenic and Antimonic Acids, Paper Presented to 4th Int. Congr.
Surf. Activ, Brussels, and Preprint C/VI.3.
Kirillova, E.A., Yusupov, T.S., 1990. Influence of mechanical activation of flotation of
cassiterite. Soviet Min. 26 (1), 81–84, January–February.
Kitto, Paul A., 1998. Renison-style carbonate-replacement Sn deposit. AGSO J. Austr.
Geol. Geophys. 17 (4), 163–168.
Klintsova, A.P., Barsukov, V.L., 1973. Solubility of cassiterite in water and in aqueous
NaOH solutions at elevated temperature. Geochem. Int. 10 (5), 540–547.
Kotlyarevsky, I.L., Alferiev, I.S., Krasnukhina, A.V., Pomazov, V.D., Egorov, N.W.,
1984. New Phosphoro-organic collectors for flotation of non sulfide mineral. In:
Jones, M.J., Oblatt, R. (Eds.), Reagents in Mineral Industry. Institution of Mining
and Metallurgy, London, pp. 173–179.
Kragten, J., 1975. The complexometry of tin (IV). Talanta 22, 505–510.
Kroll-Rabotin, Jean-Sebastien, Bourgeois, Florent, Climent, Eric, 2013. Physical
analysis and modeling of the Falcon concentrator for beneficiation of ultrafine
particles. Int. J. Miner. Process. 121, 39–50.
Lepetic, V.M., 1987. Cassiterite flotation: a review. In: Somasundaran, P. (Ed.),
Advances in Mineral Processing. SME Inc., Littleton, pp. 343–350 (Chapter 19).
Liu, Siqing, Cao, Ye, Tong, Xiong, Li, Peng, 2011. Beneficiation of a fine-sized
cassiterite bearing magnetite ore. Miner. Metall. Eng. 28 (2), 88–93, May.
Lutwick, G.D., Ryan, D.E., 1954. Aromatic hydroxylamines as organo-analytical
reagents. Can. J. Chem. 32 (10), 949–955.
Lyle, S.J., Shendrikar, A.D., 1965. A separation scheme for gallium, indium, thallium,
germanium, tin and lead by solvent extraction with N-Benzoyl-N-phenyl
hydroxylamine. Anal. Chim. Acta 32, 575–582.
Lyle, S.J., Shendrikar, A.D., 1966. Some aspects of N-Benzoyl-hydroxylamine and
Cupferron reactions with tin, antimony and other selected elements. Anal.
Chim. Acta 36, 286–297.
200 S.I. Angadi et al. / Minerals Engineering 70 (2015) 178–200
Marabini, A.M., 1978. Study of adsorption of salicyladehyde on cassiterite. Trans.
Inst. Min. Metall. 87, C76–C78.
McFadzean, B., Mhlanga, S.S., O’Connor, C.T., 2013. The effect of thiol collector
mixtures on the flotation of pyrite and galena. Miner. Eng. 50–51,
121–129.
Metals X, 2014. Renison Tin Project <http://www.metalsx.com.au/tin> (accessed
09.07.14).
Mineral Commodity Summaries, 2013. Tin, <http://minerals.usgs.gov/> (accessed
04.02.14).
Moncrieff, A.G., Lewis P.J., 1977. Treatment of Tin Ores. Transactions Institution of
Mining and Metallurgy, vol. 86, p. A56.
Moncrieff, A.G., Noakes, F.D.C., Viljoen, D.A., Davey, J.M., Boulter, G.N., 1973.
Development and operation of cassiterite flotation at mines of the Consolidated
Gold Fields. In: M.J. Jones (Ed.), 10th International Mineral Processing Congress,
London, IMM, p. 565.
Moon, S.H., Park, H.I., Ripley, E.M., Lee, I., 1996. Mineralogic and stable isotope
studies of cassiterite greisens mineralization in the Uljin area, Korea. Econ. Geol.
91, 916–933.
Mozley, R.H., Childs, G.J.C., 1992, The use of high g forces to improve both
classification and concentration in fine mineral processing. In: Invited Talk at
6th Annual Technical Meeting of Indian Institute of Metals, p. 13.
Nagaraj, D.R., 1988, The chemistry and application of chelating or complexing
agents in mineral separations. In: Somasundaran, P., Moudgil, Brij M. (Eds.),
Reagents in Mineral Technology, Surfactant Science Series, vol. 27, p. 281. ISBN:
0-8247-7715-8.
O’Connor, D.J., Buchanan, A.S., 1953. Electrokinetic properties of cassiterite. Austr. J.
Chem. 6, 278–293.
Oliverira, J.F., Adamian, R., 1992. Physico-chemical factors affecting the separation
of cassiterite and fluorite by froth flotation. Miner. Process. Extract. Metall. Rev.
9, 125–134.
Parsonage, P., Marsden, A., 1987. The influence of the structure of reagents on their
effectiveness as dispersants for cassiterite suspensions. Int. J. Miner. Process. 20,
161–192.
Polkin, S.I., Discussion on flotation research. In: Proceedings of 5th International
Mineral Processing Congress, London, IMM, 1960, pp. 361–370.
Polkin, S.I., Zhavoronok, V.I., Solnyshkin, V.I., Lunin, V.D., 1967. In: Plaksin, Igor. N.
(Eds.), Flotation Properties of Rare Metal Minerals. Primary Sources (NY), pp.
57–60 (English Text).
Polkin, S.I., Laptev, S.F., Matsuev, L.P., Adamov, E.V., Krasnukhina, A.V., Purvinskii,
A.F., 1974. Theory and practice in the flotation of cassiterite fines. In: Jones, M.J.
(Ed.), 10th International Mineral Processing Congress, London, IMM, pp. 593–
614.
Pradip, P., 1987. Surface chemistry and applications of alkyl hydroxamate collectors
on semi-soluble minerals Part II: Effect of temperature on adsorption. Colloids
Surf. 15, 137–146.
Qin, Wenqing, Yangbao, Xu, Liu, Hui, Ren, Liuyi, Yang, Congren, 2011. Flotation and
surface behavior of cassiterite with salicylhydroxamic acid. Ind. Eng. Chem. Res.
50 (18), 10778–10783.
Qin, Wen-qing, Ren, Liu-yi, Wang, Pei-pei, Yang, Cong-ren, Zhang, Yan-sheng, 2012.
Electro-flotation and collision-attachment mechanism of fine cassiterite. Trans.
Nonferrous Met. Soc. China 22, 917–924.
Raghavan, S., Fuerstenau, D.W., 1975. The adsorption of aqueous octyl hydroxamate
on ferric oxide. J. Colloid Interf. Sci. 50 (2), 319–330.
Rao, N.K., 1992. The challenges involved in the exploitation of low grade tin
deposits of India. Trans. Indian Int. Met. 45 (2), 127–138.
Rao, G.M., Subrahmanyan, N.N., 1986. Beneficiation of tungsten ores in India –
problems, processes, applications, and demands in general on a global scene.
Fizykochemiczne Problemy Mineralurgii 18, 23–37.
Richards, R.G., MacHunter, D.M., Gates, P.J., Palmer, M.K., 2000. Gravity separation
of ultra-fine (0.1 mm) minerals using spiral separators. Miner. Eng. 13 (1),
65–77.
Rinelli, G., Marabini, A.M., Alerse, V., 1976. Flotation of cassiterite with
Salicylaldehyde as acollector. In: Fuerstenau, M.C. (Ed.), Flotation – A.M.
Gaudin Memorial Volume. AMIE, New York (N.Y.), pp. 549–560 (Chapter 19).
Ruiz, F.A., Dun, I.G.H., Panuera, J.D., Calero, R.H., Longley, R., March 2004. In: Line
pressure jig (Gekkos) Starts the Modernisation Plan at the San Rafael plant,
Gravity ’04, Perth, Australia.
Ryaboi, V.I., Shenderovich, V.A., Strizhev, E.F., 1980, Protolytic dissociation of
alkylhydroxamic acids and their derivatives, Zh. Fiz. Khim., 54, No. 5, pp. 1279–
1281 (Russian Text); Russian J. Phys. Chem., vol. 54, No. 5, 1980, pp. 730–731.
Ryan, D.E., Lutwick, G.D., 1953. N-benzoylphenylhydroxylamine as a reagent for tin.
Can. J. Chem. 31 (1), 9–12.
Senior, G.D., Poling, G.W., 1986. The chemistry of cassiterite flotation. In:
Somasundaran, P. (Ed.), Advances in Mineral Processing. SME/AIME, Littleton,
pp. 229–254.
Senior, G.D., Poling, G.W., Frost, D.C., 1989. Surface contaminants on cassiterite
recovered from an industrial concentrator. Int. J. Miner. Process. 27, 221–242.
Shenderovich, V.A., Ryaboi, V.I., Kriveleva, E.D., Coin, B., Vainshenkar, V.I., Dogadina,
A.V., 1979, Influence of structural characterstisation of hydroxamic acids on
their dissociation and complex formation. J. General Chemistry of USSR, vol. 49
(Part I), 8, p. 1530.
Sivamohan, R., 1990. The problem of recovering very fine particles in mineral
processing. Int. J. Miner. Process. 28 (3–4), 247–288.
Sreenivas, T., 1997, Surface Chemical Studies on the Flotation of Cassiterite with
Alkyl Hydroxamates and Its Application on a Low Grade Indian tin ore, PhD
Thesis submitted to the University of Mumbai.
Sreenivas, T., Manohar, C., 1998. Investigations on the collector reagent
development for the recovery of cassiterite from the gravity tails of a low
grade Indian tin ore. Miner. Process. Ext. Metall. Rev. 19, 461–479.
Sreenivas, T., Manohar, C., 1999. Studies on the application of alkyl hydroxamates in
the flotation of cassiterite from an Indian tin ore. Trans. Indian Inst. Met. 52 (1),
13–22.
Sreenivas, T., Manohar, C., 2000. Adsorption of octyl hydroxamic acids/salts on
cassiterite. Miner. Process. Ext. Metall. Rev. 20, 503–519.
Sreenivas, T., Padmanabhan, N.P.H., 2002. Surface chemistry and flotation of
cassiterite with alkyl hydroxamates. Colloid Surf. A: Phys.–chem. Eng. Aspects
205, 47–59.
Sreenivas, T., Srinivas, K., Natarajan, R., Padmanabhan, N.P.H., 2004. An integrated
process for the recovery of tungsten and tin from a combined wolframite–
scheelite–cassiterite concentrate. Miner. Process. Extract. Metall. Rev. 25, 193–
203.
Srinivas, K., Sreenivas, T., Natarajan, R., Padmanabhan, N.P.H., 2000. Studies on the
recovery of tungsten from a composite wolframite–scheelite concentrate.
Hydrometallurgy 50, 43–50.
Trahar, W.J., 1981. A rational interpretation of the role of particle size in flotation.
Int. J. Miner. Process. 8, 289–327.
Turner, J.W.G., Hallewell, M.P., 1993. Process improvement for fine cassiterite
recovery at Wheel Jane. Min. Eng. 6 (8–10), 817–829.
Veasey, T.J., Penhallow, A.L., Elliott, A.J., 1989. Mineralogy and mill performance
optimization – a case study of south crofty tin mine. Miner. Eng. 2 (4), 471–480.
Victory Mines, 2014. South American Tin Projects, <http://www.victorymines.com/
investors-publications/> (accessed 09.07.14).
Vivian, A.C., 1927. Flotation of tin ores. Min. Mag. 36, 348.
Wang, Pei-pei, Qin, Wen-qing, Ren, Liu-yi, Wei, Qian, Liu, Rui-zeng, Yang, Cong-ren,
Zhong, Shui-ping, 2013. Solution chemistry and utilization of alkyl hydroxamic
acid in flotation of fine cassiterite. Trans. Nonferrous Met. Soc. China 23, 1789–
1796.
Warren, L.J., 1982. Flocculation of stirred suspension of cassiterite and tourmaline.
Colloids Surf. 5, 301–319.
Wells, A.F., 1975. Structural Inorganic Chemistry. Clarendon Press, Oxford.
Wills, B.A., Napier-Munn, T.J. October 2006, Elsevier Science & Technology Books,
ISBN: 0750644508, Mineral Processing Technology, An Introduction to the
Practical Aspects of Ore treatment and Mineral Recovery, p. 4.
Wottgen, E., 1969. Adsorption of phosphonic acids on cassiterite. Transact. Inst.
Min. Metall. 78, C91–C97.
Wu, X.Q., Zhu, J.G., 2006. Selective flotation of cassiterite with benzohydroxamic
acid. Miner. Eng. 19, 1410–1417.
Xu, Yang-bao, Qin, Wen-qing, Liu, Hui, 2012. Mineralogical characterisation of tin-
polymetallic ore occurred in Mengzi, Yunnan Province, China. Trans. Nonferrous
Met. Soc. China 22, 725–730.
Yale, Y.L., 1943. The hydroxamic acids. Chem. Rev. 33, 209–256.
Zambrana, G.Z., Medina, R.T., Guierrez, G.B., Vargas, R.R., 1974. Recovery of minus
ten micron cassiterite by liquid – liquid extraction. Int. J. Miner. Process. 1, 335–
345.
Zeng, Qing-hau, Zhao, Hong, Wang, Dian.-zuo, 2000. Influence of metal cations on
cassiterite flotation. Trans. Nonferrous Met. Soc. China 10 (1). Article ID: 1003-
6326(2000)01-0098-04, February.
Zhou, Yongcheng, Tong, Xiong, Song, Shaoxian, Wang, Xiao, Deng, Zhengbin, Xie,
Xian, 2014. Beneficiation of cassiterite fines from a tin tailing slime by froth
flotation. Separat. Sci. Technol. 49 (3), 458–463.