A Review of Cassiterite Beneficiation Pratices

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 Salas, 1977; Lepetic, 1987; Senior and Poling, 1986; Sreenivas,
1997; Sreenivas and Manohar, 1998, 1999, 2000; Sreenivas and
The important properties of tin such as malleability, ductility, Padmanabhan, 2002; Bulatovic, 2010). During the 1970s, specific
and resistance to corrosion make it suitable for use in variety of collectors for cassiterite such as arsonic acid, and phosphonic acid
applications. Tin was alloyed with copper to form bronze metal were used in the operating plants; later, the usage ceased due to
that found wide applications such as making weapons, metal economic and environmental concerns. Many more collectors have
objects and sculptures and cutting tools during the Bronze Age been found which are suitable for cassiterite flotation such as oleic
(Chakrabarti and Lahiri, 1996). The melting point of the metal is acid, alkyl phosphoric acid, hydroxamates, succinamate phospho-
very low, about 232 °C. When alloyed with lead, the melting point ric ester, sodiumhylenesulponate and the use of such reagents
further reduces to 183 °C, and the alloy is largely used in soldering has been documented in a number of articles (Lyle and
in electronic and plumbing applications. The metal finds many Shendrikar, 1966; Wottgen, 1969; Moncrieff et al., 1973; Rinelli
more applications in chemical, alloy making, decorative metals, et al., 1976; Marabini, 1978; Doren et al., 1979; Kotlyarevsky
etc. The consumption of the metal is rising day-by-day due to et al., 1984; Baldauf et al., 1985; Cheng and Zhu, 1986;
increased end uses. Parsonage and Marsden, 1987; Gruner and Bilsing, 1992;
Cassiterite is the prime mineral from which tin metal is Khangaonkar and Kamarudin, 1994; Qin et al., 2011; Wang et al.,
extracted economically. The mineral is heavy, hard, extremely brit- 2013). The flotation recovery of cassiterite decreases with a
tle in nature, and is generally associated with lighter gangue min- decrease in particle size and in practice ultrafine particles are often
erals. It is reported that about 80% of the world tin reserves are removed prior to flotation. Attempts have been made to recover
placer/alluvial deposits (Falcon, 1982, 1985; Wills and Napier- such fine and ultrafine cassiterite values following physico-chem-
Munn, 2006, Tin-Indian Mineral Year Book, 2010). Such types of ical separation techniques such as shear flocculation (Bilgen
ores are easy to beneficiate following gravity units due to their et al., 1994), spherical agglomeration (Farnand et al., 1964), selec-
coarse liberation size (Moncrieff and Lewis, 1977). The cassiterite tive flocculation (Clauss et al., 1976), liquid–liquid extraction
occurring in hard-rock deposits is associated with granitic host (Zambrana et al., 1974) and electro-flotation (Hogan et al., 1979;
rock that needs comminution, classification, gravity concentration, Qin et al., 2012; Gonzales et al., 2013), and such attempts are still
and flotation techniques to beneficiate. The minerals associated in the laboratory scale.
with such types of deposits are harder to beneficiate because of Cassiterite beneficiation plants all around the world have
fine liberation size. Cassiterite beneficiation flowsheets generally undergone many developments in terms of modifications in the
consist of gravity separation units and flotation cells to upgrade conventional flowsheets, incorporation of newly invented equip-
the raw material to a marketable grade concentrate (Collins ment, and in revision and adoption of novel chemical reagents,
et al., 1968; Polkin et al., 1974; Moncrieff and Lewis, 1977; Burt, etc. Most of these developments have been market driven. Several
1984; Falcon, 1985; Baldauf et al., 1985; Senior and Poling, 1986). research articles (Burt and Ottley, 1974; Turner and Hallewell,
Numerous types of gravity separators are used in the concentra- 1993; Beniuk et al., 1994; Ruiz et al., 2004) highlight implementa-
tion of tin ores. Units such as jigs, spirals, and tables are used in the tion of advanced gravity separators to treat cassiterite fines. Burt
primary concentration stage, and the final concentrate can be and Ottley (1974) reported the use of the Bartles-Mozley concen-
achieved using enhanced gravity concentrators or flotation cells. trator to treat heavy mineral particles; the unit was used to pre-
Many enhanced gravity concentrators have been developed in concentrate cassiterite at Ecstall Mining Ltd., Ontario, wherein tin
the recent past to address the complex issues of beneficiation. values were distributed in all size fractions, and the separator
These enhanced gravity concentrators make use of centrifugal or could recover values down to 10 lm. Falcon (1982) studied the
other additional forces to increase the separation efficiency. Parti- efficiency of different gravity concentrators treating cassiterite
cle size plays a major role in gravity concentration (Burt, 1988); the fines. Turner and Hallewell (1993) discussed in detail plant scale
separation efficiency is very high for coarse particles while it drops modifications with respect to reagent scheme, installation of a flo-
down considerably for fine sizes. The efficiency of different gravity tation column, and a Mozley multi-gravity separator in upgrading
concentrators treating tin ores has been investigated by many the product quality to 60% Sn at the Wheal Jane plant, UK. Simi-
researchers (Falcon, 1982; Burt, 1984, 1988; Turner and larly, Beniuk et al. (1994) discussed the application of the Kelsey
Hallewell, 1993), and it is reported that advanced gravity concen- centrifugal jig in upgrading the product quality and elimination
trators could recover particle size down to 3 lm. of the acid leaching plant at the Renison tin concentrator, Australia.
A typical gravity concentration circuit recovers about 50–60% In the current review paper, an attempt has been made to sum-
cassiterite (Lepetic, 1987) but significant values in the fine size marize overall developments, which have occurred in gravity con-
are lost in the gravity tailings. Application of flotation and develop- centration and flotation techniques for the beneficiation of
ment of selective collectors have made it possible to recover fine cassiterite. The influence of particle size on gravity concentration
cassiterite from the gravity tailings, which has resulted in improve- and flotation techniques is revisited, and surfactants in cassiterite
ment of overall plant recovery values to over 80%. A substantial flotation are thoroughly reviewed. Tin beneficiation plant practices
amount of research work on cassiterite flotation has been reported are discussed and subsequent improvements in preparing higher
in the past four to five decades (Polkin et al., 1974; De Cuyper and 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- Brazil
tance; it occurs in alluvial/placer deposits as well as primary Bolivia
200
hard-rock deposits (Falcon, 1982). Tin occurrence in alluvial/placer Russia
deposits is due to weathering of primary hard-rocks followed by 150 Peru
transportation of eroded material. The heavy and chemically resis- Malaysia
tant tin easily form residual concentration and such deposits are 100 Australia
mostly located in South East Asian continents, particularly in
Thailand
Malaysia, Indonesia and Thailand. The primary hard-rock deposits 50
Others
are of late-stage granitic intrusions found in veins and fissures in
the granite and surrounding country rocks. The hard-rock deposits 0
are predominant in China, South America and Australia. 1970 1975 1980 1985 1990 1995 2000 2005 2010
The estimated tin metal resources in the world is about 4.9 mil- Year of production
lion tonnes, which is distributed in China (30.5%), Indonesia
Fig. 1. Tin world mine production 1970–2010 (ITRI Briefing, 2011).
(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 quantity of tin during 1970s, while the consumption rate remained
production and distribution of tin. 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-
2.1. Production sumed about 52% of the tin produced followed by tin plates and
chemical industries during 2006. It is reported (ITRI Briefing,
The strategic metal tin production was almost stable at about 2011) that world consumption of tin from 1960 to 2000 main-
200 tonnes per annum during the post-war period and finds many tained a plateau of 200,000–250,000 tonnes and 2000 onwards it
ups and downs in 1960–1990 due to fluctuations in the interna- has raised to 350,000 tonnes.
tional market price. The world production of tin reached as high
as 325,000 tonnes in 2005 due to increased demand. Around
3. Tin minerals
244,000 tonnes of tin production reported in 2011 of which about
80% comes from China, Indonesia and Peru. World reserves and
Tin is preferentially concentrated during magmatic differentia-
mine production of different countries is presented in Table 1.
tion process and shows affinity for granitic rocks and their extru-
Fig. 1 shows the world mine production from 1970 to 2010. It
sive equivalence. Table 2 shows the list of tin minerals that occur
can be observed from the figure that the refined tin metal produc-
in the earth crust, of these the only economic mineral is cassiterite
tion varies year by year with respect to different countries, but
(SnO2). The physical and chemical properties of cassiterite are
average production from all countries shows an increasing trend.
given in Table 3. The economic deposits of cassiterite are known
The cumulative production of maximum tin accounts for China,
in two types of geological occurrences – primary vein or hard-rock
Indonesia, Brazil, Bolivia, and Peru. Since the 1990s, there is no
deposits and secondary placer deposits (Falcon, 1982; Rao, 1992).
report of smelting of tin metal from US and European producers.
The mineral assays about 0.4–1.5% Sn (occasionally 5–6%) in the
About 15% of the world production accounts from the secondary
hard-rock deposits and placer deposits are slightly poorer in grades
materials that reports from Belgium and China.
(Bulatovic, 2010). Pure cassiterite theoretically accounts 78% Sn.
Typical concentrate grades vary between 65% and 78% Sn contents
2.2. Consumption due to the presence of various mineral impurities containing the
elements such as tantalum, niobium, titanium and others.
Tin consumption by different sectors is varying with time. Tin Cassiterite occurring in the placer type deposits is often coarse
plate industries in USA and European countries consume the major 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
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
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.

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-

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
Fig. 3. Recovery-size curve for fine gravity separators (Burt, 1984). review, fundamental components pertaining to the cassiterite flo-
tation are discussed in detail.
concentrator, Bartles-Mozley separator, and slime table are very
efficient for the beneficiation of tin ores. 6.1. Cassiterite surface properties
Selection of processing units for the beneficiation of tin ores is
very important (Jeon et al., 2012). It is reported that one-third of The chemical formula of cassiterite is SnO2. It possesses a
tin mined in Bolivia is wasted in plant tailings (A Bandopadhyay, tetragonal structure, 6:3 coordination with oxide anions arranged
2000), which is mainly attributed due to lower efficiency of the in octahedral around a stannic ion (Wells, 1975; O’Connor and
gravity concentrators and flotation units in treating ultrafine tin. Buchanan, 1953). Pure cassiterite is almost chemically inert, and
Turner and Hallewell (1993) described metallurgical improve- is highly insoluble i.e. the concentration of constituent ions in solu-
ments achieved due to insertion of Mozley multi-gravity separator tion is negligible (Edwards and Ewers, 1951; Kragten, 1975;
as the final stage of cleaning in place of existing flotation column at Barsukov and Klintsova, 1970; Klintsova et al., 1973) as shown in
Wheal Jane plant UK. The multi-gravity separator was capable of Table 5.
recovering fine cassiterite values in the size range 45–6 lm. Details Cassiterite, when placed in aqueous medium undergoes
of Wheal Jane plant operations are discussed in the subsequent hydroxylation as shown below:
sections. SnO2.nH2O(solid)
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- Sn(OH)6-2 Sn(OH)5- Sn(OH)4 Sn(OH)3+ Sn(OH)2+2 Sn(OH)+3 Sn+4
ing of middlings and rougher concentrates, and also it is capable to
separate particle size down to 20 lm and finer. SnO2 ðcrystallineÞ þ 2H2 O ðliqÞ
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- The equilibrium constant, pK298.15, of the reaction is reported as
tration tailings. Many developments in the gravity concentration 59.7 ± 0.5. The equilibrium constant for freshly precipitated tin
equipment design have been observed during 70s and 80s for hydroxide at 20 °C is reported to be 56, and for the aged tin
treating fine to ultrafine particles. The units such as Bartles–Moz- hydroxide it is 61.
ley separator, Bartles cross-belt separator, Mozley multi-gravity From the investigations on the solubility of stannic oxide in
separator, Falcon UF separator etc. were found efficient in the ben- water at 25 °C, it was found that in the pH range 2–11 solubility
eficiation of fine tin particles. does not depend on the pH and a neutral molecule is formed that
Falcon Ultra-Fine (UF) separator is used for the concentration of dissolves, which is shown below:
heavy minerals present in the ultra-fine (up to 3 lm) particles SnO2 þ 2H2 O
SnðOHÞ4
(Kroll-Rabotin et al., 2013). Generally, the heavy mineral content
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.
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.
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 phosphonic acid was the most efficient. Optimum results were
The identification of p-tolyl arsonic acid as a selective collector obtained with the alkyl phosphonic acids of chain length C5–C7
for cassiterite was a major catalyst to introduce flotation in many (Wottgen, 1969). The work by Collins et al. (1968) concluded that
tin mines around the world (Senior and Poling, 1986). The com- aryl phosphonic acids are more selective compared to alkyl phos-
mercial production of this reagent was ceased in the free world phonic acids. The microflotation studies indicated that maximum
market after 1975 due to its high cost and environmental concern. cassiterite recovery observed with phosphonic acid collectors
However, the high selectivity of arsonic acid based reagents for between pH 2 to 3, which decreases rapidly at lower pH. The flota-
cassiterite made it suitable to be used even now in cassiterite flo- tion response gradually decreases from pH 3 to 7, beyond pH 7 it
tation plants in China in the form of MTAA (50:50 mixture of o- drops rapidly. However, plant experience showed interruptions
and p-toly arsonic acid). The optimum pH for flotation with arsonic in flotation below pH 4 (Senior et al., 1989). It was observed that
acid is generally laying in the region pH 3.7 to 8.5. An unusual fea- phosphonic acids are efficient at particle size finer than 40 lm
ture of the arsonic acid flotation is its inability to recover particles and are also efficient for cassiterite that occurs along with high iron
coarser than 40 lm. content.
Kotlyarevsky et al. (1984) synthesised and tested a variety of
6.2.3. Phosphonic and diphosphonic acids substituted diphosphonic acids for cassiterite ores. These authors
A significant advancement in cassiterite flotation has been the used p-electron donor compounds with low polarity to enhance
development of new class of collectors – the alkyl and aryl phos- the hydrophobicity in conjunction with diphosphonic acids. Based
phonic acids. It was established by Kirchberg and Wottgen on their results it was found that 1-hydroxyalkylidene-1, 1-diphos-
(1964) that of various aryl compounds tested, p-ethyl benzene phonic acid (Flotol-7, 9) with 7–9 carbon atoms produced best col-
lection properties for cassiterite. Flotol-7, 9 exhibits a wide range 6.2.5. Hydroxamic acids and their tin complexes
of differentiation in terms of collecting properties for cassiterite Hydroxamic acids are regarded as derivatives of both hydroxyl
and other rock forming minerals (tourmaline, ferrous oxide and amine and carboxylic acids, which can be represented by the gen-
garnet). In addition, unavoidable ions in flotation pulp such as tri- eral formula ARACOANHOH (Yale, 1943; Agarwal, 1979; Brandt,
valent iron and aluminium have a negligible effect on cassiterite 1960). A striking feature of hydroxamic acids is their ability to form
flotation with Flotol-7, 9. Flotation experiments on an ore contain- coordination compounds (Chatterjee, 1978). As a bidentate group,
ing 0.56% Sn with Flotol-7, 9 gave a concentrate analyzing 25.6% Sn the anionic hydroxamate resembles the acetylacetonato ligand,
with 83% recovery. Other cassiterite collectors (styrene phosphonic CH3ACOACH2ACOACH3, in its behaviour towards various metal
acid, sulphosuccinamate and hydroxamic acid) gave equal recovery ions. The pKa of the usual alkyl hydroxamic acid is close to 9
with much inferior concentrate grade. The reagent consumption in (Ryaboi et al., 1980). It has been established that the protons disso-
the case of Flotol-7, 9 is less, by half, compared to other collectors. ciate from the oxygen attached to nitrogen, giving the structure of
Similar performance was observed by Houot and Desbrosses hydroxamate anion, RCONHO (Fuerstenau, 1984). However few
(1991) when tested on a complex sulphide polymetallic ore con- researchers (Exner, 1968) have reported that most of the hydroxa-
taining 5.8% Sn. About 50% of cassiterite was recovered with a con- mic acids belong to the N-acid type rather than O-acid type; i.e.,
centration ratio of 12, using 400 g/t of dodecane diphosphonic acid the hydrogen attached to the nitrogen atom is acidic than the
at pH 5. one attached to the oxygen.
Gruner and Bilsing (1992) reported the use of styrene phos- According to the existing concepts, hydroxamic acids can disso-
phonic acid in the laboratory flotation of different tin ores collected ciate in accordance with the scheme given in Fig. 5 (Shenderovich
from Czechoslovakia, Canada, Portugal and Germany. Also, this et al., 1979). Existence of the forms III and IV has been shown most
reagent has been introduced into the processing plants at Neves convincingly for benzohydroxamic acid in solution, in all other
Corvo, Portugal, Rio Kemptville, Canada and Altenberg, and Ger- cases these forms have merely been regarded as possible alterna-
many. The results show that styrene phosphonic acid is suitable tives, and only in application to aromatic acids. For aliphatic
for the flotation of finely disseminated cassiterite and wolframite hydroxamic acids such data are absent. It has also been well estab-
ores, and it is possible to obtain a high-grade concentrates of more lished that tautomerisation of hydroxamic acids to the enol form -
than 40% Sn with high recovery values. RC(OH)@N(OH) does not occur to any appreciable extent (Hadzi
and Prevoesek, 1957).
Complexes of hydroxamic acids of differing stabilities with
6.2.4. Sulphosuccinamate metal ions such as Nb, Ti, Mn, V, Zr, Hf, Ta, Fe, Cu, Co, Sn, Al, rare
The first recorded use of sulfosuccinamate as a collector for cas- earths have been reported (Brandt, 1960). Rather strong complexes
siterite was at Wheal Jane concentrator, Cornwall, UK (Senior and are formed with the highly charged rare-earth elements and alumi-
Poling, 1986; Lepetic, 1987). While the selectivity of the reagent num; the strongest complexes are formed with Fe+3 and probably
was inferior to arsonic acid, it was less toxic, biodegradable and with Ta+5 and Nb+5. Weakest complexes are with alkaline earth
cheaper than arsonic acid, which led to its wide-spread usage in metal cations like Ca+2 and Ba+2 (Pradip, 1987; Bogdanov et al.,
many plants. In his original patent, Arbiter (1968) stated that flota- 1977). Since there is a definite evidence for the existence of intra-
tion of cassiterite with sulfosuccinamate was best carried out at pH molecular hydrogen bonding in hydroxamic acids, as given in
value < 2.5, and that is a pH well below the isoelectric point of cas- Fig. 6a, the structure given in Fig. 6b has been considered to be very
siterite. Published micro-flotation test results (de Cuyper and Salas, reasonable for their metal complexes (Raghavan and Fuerstenau,
1977; Zambrana et al., 1974) confirm that recovery reaches a max- 1975). However, studies by Russians (Shenderovich et al., 1979)
imum well below the cassiterite isoelectric point and drops signif- on the influence of structural characteristics of hydroxamic acids
icantly when the zeta potential of the mineral decreases and on their dissociation and complex formation indicates that aro-
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- Fig. 6. (a) Intramolecular hydrogen bonding in alkyl hydroxamic acids and (b)
eral surface is positively charged. mode of complexation of alkyl hydroxamate anion with metal ion.
Fig. 5. Dissociation equilibria of hydroxamic acid in water, R – aryal or alkyl group (Shenderovich et al., 1979).
matic hydroxamic acids have a different character of dissociation coordination of tin ion was through two oxygen atoms in the
because of the strong inductive effect of the phenyl substituent ligand molecule as given in Fig. 8. The possibility of coordination
on NH group than OH group. Thus in the Nuclear Magnetic Reso- through nitrogen and oxygen atoms is rejected on the ground that
nance (NMR) spectrum of potassium salt of benzohydroxamic acid resulting structure is a four-membered chelate ring, which is not
the signal of a proton of NH group is absent while the signal for the favored thermodynamically.
proton of OH is retained, which confirms the presence of species IV The formation of such a complex made them (Shenderovich
(Fig. 5) in solution. et al., 1979) to advocate that the mixture of anions as shown in
Structural characterization of tin (IV) complexes of aromatic and Fig. 9 in a solution will be in dynamic equilibrium. They
aliphatic hydroxamic acids were studied in detail by several (Shenderovich et al., 1979) have also reported that the type of com-
researchers (Shenderovich et al., 1979; Lyle and Shendrikar, 1966, plexation given by them is in keeping with the concepts of molec-
1965). A derivative of hydroxamic acid, N-Benzoylphenylhydroxyl- ular-orbital theory. The p orbitals of adjacent nitrogen and oxygen
amine (BPHA), was used to quantitatively precipitate tin, both atoms of the hydroxamate grouping form common orbitals, one of
stannous and stannic (Ryan and Lutwick, 1953; Lutwick and Ryan, which has greater and other less energy. The p⁄ orbital of higher
1954). The infra-red spectra of the precipitated complex energy, which includes a contribution of the atomic orbitals of oxy-
indicated the formation of an inner complex of the composition gen, on complex formation overlaps to a greater extent than the
Sn(C13H10O2N)2Cl2 and not an addition compound. The spectra also orbital of nitrogen with the vacant orbital of the metal.
show that the tin compound appeared to contain hydroxyl Many researchers (Sreenivas and Manohar, 2000; Sreenivas and
hydrogen of BPHA and tin is combined with carbonyl oxygen, as Padmanabhan, 2002; Wang et al., 2013) have studied surface
given in Fig. 7. chemistry and flotation characteristics of cassiterite with alkyl
NMR studies by Shenderovich et al. (1979) on the heavy metal hydroxamic acids/salts. Investigation results show that octyl
salts of hydroxamic acids formed with aliphatic derivatives indi- hydroxamic acid adsorbs on the cassiterite surface by physical
cate the presence of anion of from V (Fig. 5). The analogues nature and specific forces. The maximum adsorption occurs at acidic pH
of the IR spectra of iron and tin hydroxamates led them due to involvement of surfactant and uncharged and/or moder-
(Shenderovich et al., 1979) to conclude that the most probable 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-
Fig. 7. Structure of tin benzophenylhydroxamic acid complex (Shenderovich et al.,
ited as of now, since, the mechanism of collector interactions in
1979). 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
Fig. 8. Suggested mode of complexation of alkyl hydroxamate anion to stannic ion 25% from the ore containing 2.5% Sn. Cupferron forms O and O type
(Shenderovich et al., 1979).
metal chelates and the arrangement of the atoms in the molecule
Fig. 9. Structures of alkyl hydroxamate anion in dynamic equilibrium in water medium (Shenderovich et al., 1979).
follows AOA and AN@O. This reagent is considered specific for upgrade SnO2 content to 90% in the concentrate from the feed
Fe(II) and Cu(II), but it forms chelates with several other metals containing 58% with 90% removal of impurities.
including Sn(IV) (Nagaraj, 1988). Arslan et al., 2002 developed a processing flowsheet for the
Polkin et al. (1974) reported the efficacy of di-(2-ethyl) hexyl recovery of Cu and Sn from the copper refining slag collected from
phosphoric acid ester (DEHPA) on flotation of fine cassiterite ores Sarkuysan A.S. that contain about 22% Cu and 2.3% Sn. The
having complex composition [ferruginized quartz (50–60%), tour- flowsheet includes comminution, classification, flotation and
maline (30%) and iron hydroxide (10%)]. The experimental result leaching stages to recover Cu and Sn values.
shows higher flotation performance at pH 3–3.5. The consumption Ibezim-Ezeani and Anusiem, 2011 studied the thermodynamics
of DEHPA at rougher flotation stage was 0.7–0.8 kg/ton. The ratio of of adsorption of palmitate and laurate soaps onto galena, hematite
concentration of Sn was 10–18 with 50–65% recovery. and cassiterite surfaces, wherein, different isotherm models were
Use of salicylaldehyde in the flotation of cassiterite was used to evaluate the adsorption capacities. The Langmuir isotherm
reported by Rinelli et al. (1976) and Marabini (1978). Results show model gave best fit to the experimental data with monolayer
that the concentrate assaying 1.5% Sn with 88% recovery was adsorption capacity values following the order galena > hema-
obtained from an ore containing 0.4–0.5% Sn. However, the reagent tite > cassiterite for both (palmitate and laurate) soaps. Computa-
consumption was very high (8–10 kg/ton). It was also observed tion of Gibbs free energy (DG), enthalpy (DH) and entropy (DS)
that the recovery enhanced to 95% with the grade of 2.5% Sn, when indicated that the adsorption process is spontaneous, exothermic
same quantity of salicyaldehyde was added during the grinding and is predominantly physisorption.
stage. Liu et al., 2011 have developed beneficiation flowsheet for a
Doren et al. (1979) studied the influence of non-ionic surfac- fine-sized cassiterite bearing magnetite ore collected from Sichuan
tants on the flotation of cassiterite. The investigation results show province, China containing 0.39% Sn and 23.20% Fe. The character-
a favourable influence of the combination of sulfosuccinamate- isation studies indicated that 90% cassiterite values found liberated
alkyl polyoxyethylene on selectivity and recovery of tin flotation at – 0.01 mm size. Beneficiation flowsheet incorporating commi-
at pH 4.5 (isoelectric point of cassiterite). nution, magnetic separation (two stage), and shaking table could
Kirillova and Yusupov (1990) have studied the influence of separate iron concentrate (assays 61.69% Fe with recovery of
mechanical activation on cassiterite flotation. The studies showed 75.09%), tin concentrate (assays 27.21% Sn with 56.97% recovery),
that mechanical activation was responsible to impart structural and sulphur concentrate (assays 40.86% S with recovery values of
defects on cassiterite with the major changes in tin-oxygen bond 32.03%).
strength and enthalpy of formation of SnO2. Qin et al., 2012 studied electro-flotation of cassiterite fines,
Cheng and Zhu (1986) reported the performance of alkyl phos- wherein, particle bubble collision and its attachment were calcu-
phorous esters on cassiterite flotation. The results of this study lated following relevant equations available in the literature.
showed that alkyl phosphorous esters are effective collectors when Gonzales et al., 2013 have studied electro-flotation of cassiterite
the alkyl group is octyl, decyl and dodecyl. Flotation studies on a fines using a bioreagent Rhodococcus opacus (R. Opacus). Surface
mixture of – 10 lm cassiterite and quartz (containing 7.1% Sn) characterisation studies such as zeta potential, contact angle, and
show that it is possible to achieve 89.9% recovery with 48.8% Sn adsorption measurements reveal the interaction between Rhodo-
content. When the experiments repeated with an undeslimed mix- coccus opacus and the cassiterite mineral. The interaction of bior-
ture of – 40 lm cassiterite and quartz (head assay of 7.5% Sn), a eagent on cassiterite fines increases the contact angle. Electro-
product of 73.5% Sn content with 95% recovery was achieved. flotation results show that the bioreagent could recover about
Oliverira and Adamian, 1992 have studied selective separation 65% cassiterite values at pH 5, concentration 2.87 1012 cells/ml
of cassiterite and fluorite using anionic collectors. The studies were (50 mg/L) and current density of 51.4 mA/cm2.
focused on adsorption, electrophoretic mobility, and suspension
stability measurements of both cassiterite and fluorite. Micro-flota- 6.3. Effect of particle size on tin flotation
tion experiment results showed that at low concentration of anio-
nic collector fluorite can be selectively floated from the cassiterite Trahar (1981) identified the role of particle size in flotation fol-
particles. lowing the data obtained from the plant survey and related labora-
Selective flotation of cassiterite from synthetic mixtures of cas- tory batch tests. It has been realised from the data that the degree
siterite-quartz and cassiterite-calcite was attempted by Wu and of hydrophobicity is a function of particle size; hence recovery-size
Zhu (2006) using benzohydroxamic acid. Micro-flotation studies curves play a valuable diagnostic tool in assessing the flotation per-
show that benzohydroxamic acid floats cassiterite particles effi- formance. The recovery-size curve shown in Fig. 10 gave in-depth
ciently than calcite and quartz. The interaction of cassiterite and information about the particle size effects in flotation, wherein,
benzohydroxamic acid have been analysed through zeta potential recovery of particular size fraction has been plotted against the
measurements and infrared spectra studies, which confirms the average size. The plot has characteristic curve divided into three
collector adsorption on the mineral surface following chemisorp- regions; fines, intermediate, and coarse. Intermediate size fraction
tion with the formation of Sn-benzohydroxamic acid. is favourable to flotation compared to fines and coarse particles.
Choi et al., 1998; Zeng et al., 2000 have studied the influence of The shape of the curve remains similar for flotation of all types
metal cations such as lead, ferric, ferrous, aluminium, manganese, of minerals; however, demarcation of these three regions would
calcium on flotation of cassiterite, wherein sulphosuccinamate was vary based on the physical and mineralogical characteristics of
used as a collector. The micro-flotation tests followed by X-ray the feed material.
photoelectron spectroscopy (XPS) analysis with and without metal Fig. 11 shows the batch flotation results on the feed sample col-
cations show that the lead ions activate the cassiterite surface lected from the Renison tin concentrator. These experiments were
whereas other cations depress the mineral surface. carried out by using p-tolyl arsonic acid (pTA) as a collector
Bulatovic and De Silvio (2000) have developed the process for (0.5 kg per tonne) at pH 5.5, these conditions are mostly influencing
the removal of zircon, tantalum and columbite impurities from the recovery of gangue minerals (siderite, tourmaline and other sil-
tin gravity concentrate following direct flotation of tin using a mix- icates) to the concentrate through entrainment (Goodman and
ture of sulphosuccinate collector modified with fatty alcohol ester Trahar, 1977). The recovery of gangue (siderite) follows a similar
sulphate and depression of impurities using organic acids and trend in the plant data. Further, it has been analysed that pTA is a
sodium silicate. Experimental results show that it is possible to weak collector for cassiterite. The required rate of flotation was
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.
Fig. 10. Influence of particle size in cassiterite flotation (Trahar, 1981).
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-
Fig. 11. Batch flotation results on cassiterite sample collected from Renison tin state tin recovery operations. Table 7 shows estimated reserves
concentrator (Trahar, 1981). with metal contents in few old tailing damps. Advanced gravity
concentration, flotation, and fuming techniques are employed to
attained in the plant by using higher collector and frother additions,
recover tin values present in the tailings.
higher pulp level and aeration rates. On the contrary, such condi-
Pilot-scale investigations carried out on Kenko and Catavi tail-
tions yield high water recovery rates to the concentrate leading to
ings indicated that it is possible to up-grade 54–56% Sn from the
the entrainment of fine gangue. Particle size analysis indicated that
feed content 0.2–0.4% Sn with significant recovery values. Investi-
96% of the feed material is finer than 20 lm and 30% is finer than
gations on Peru’s San Rafael tailings indicated that the tailing
5 lm. It is reported that the flotation efficiency was very low for
recovery project could compensate the present production losses.
the cassiterite particles <5 lm. In conclusion, feed containing 2%
Zaaiplaats tin tailing dumps in South Africa are estimated to
Sn has been upgraded to 25% Sn with 85–90% recovery.
contain 2600 to 4500 tonnes of tin. Tin values dumped in Zaaipla-
ats tailing pond due to the limitations of old processing flowsheet
6.4. Fine particle processing that consists of stamp-mills and gravity concentrators (shaking
table and spiral). Recent studies on pilot-scale Falcon UF concen-
Fine particle processing has gained considerable attention of trator followed by shaking table indicated that it is possible to
researchers due to inefficiency of the flotation to treat ultrafine recover fine cassiterite values from the tailings.
Table 7
Tin tailing projects with estimated reserves and quantity (as on July 2014).
Tailing projects Reserves (million tonnes) Assay (%) Webpage references

Renison, Australia 19.2 0.45% Sn and 0.21% Cu Metals X, Ltd. (2014)
Cleveland, Australia 3.8 0.30% Sn and 0.13% Cu Elemento,s Ltd. (2014)
Kenko, Bolivia 9.0–9.3 0.38–0.40% Sn Victory Mines (2014)
Catavi, Bolivia 19–20 0.29–0.31% Sn ITRI (2014a)
San Rafael, Peru 7.6 1.00% Sn ITRI (2014b)
Zaaiplaats, South Africa 2.6–3.2 0.08–0.197% Sn Bushveld Minerals Ltd. (2014)
Recovery of tin values from the gravity tails containing 0.24% Sn during 1950s and 1960s from the alluvial deposits were using
collected from Tosham, Haryana, India was attempted by Sreenivas washing, sizing, and gravity concentration (jigs, sluices, tables)
and Manohar (1998, 1999). Large-scale flotation experiments were techniques. The concentrate produced after a number of roughing,
carried out on the gravity tailing sample using phosphonic acid, scavenging and cleaning stages would assay marketable grade con-
sulfosuccinamate and phosphoric acid ester collectors. Experimen- centrate with relatively low recovery of tin values. This is attrib-
tal results show that it is possible to achieve a product grade of 7% uted due to fine cassiterite loss (0.4–0.8%) in the gravity tailings
Sn with recovery of about 55% from the reagent combination; (Bulatovic, 2010).
phosphoric acid ester – sodium silicofluoride – sulphuric acid Tin content in the hard-rock deposits assays 0.4–1.5% and even
and citric acid. richer in some occurrences (Bulatovic, 2010). Most of the rich
Zhou et al. (2014) studied the beneficiation of cassiterite tailing deposits are exhausted and currently very low-grade ores are pro-
slimes from Datun concentration plant following flotation with cessed. Low-grade ores are fine grained and tin values are highly
benzohydroxamic acid as a collector, lead nitrate as an activator, disseminated in the ore body. Beneficiation of such ores creates a
and pine oil as a frother. The cassiterite occurrence in the tailings number of problems including fine tin losses in the tailing stream.
is fine grained and associated with mainly iron and calcium bear- Typical recovery values from the low-grade ores would not exceed
ing minerals. In the proposed method desliming and use of disper- 50–60% Sn by gravity units, hence a combination of gravity and flo-
sant and depressant are evaded due to unwanted tin losses in the tation techniques are employed to improve the recovery values to
flotation tailings. The collector, activator, and frother combination more than 70%. In many instances, gravity concentrate contains
could enrich the Sn values to 3.5% from the feed containing 0.18% sulfides that can be removed by the flotation cells to generate
Sn with recovery values of 74–75%. the final concentrate. During 1970s and 1980s majority of the tin
Tin in low-grade ores is generally associated with iron, silica, beneficiation plants have introduced flotation circuit to recover
and alumina bearing gangue minerals. Cassiterite present in such fine tin from the gravity tailings (Turner and Hallewell, 1993;
a type of ores is in the form of fine to ultra-fine inclusions within Bulatovic, 2010). Tin beneficiation flowsheets are discussed here-
the gangue phase; as a result, it is difficult to recover fine tin values under with the salient features of the processes incorporated and
following gravity and flotation techniques. Usually, fuming is prac- changes made with the advent of new technology in attaining
ticed to recover fine tin from the low-grade ores, which facilitates higher concentrate grade and recovery.
release of cassiterite from the gangue mineral cluster following the
reactions:
Cassiterite reduction to stannous oxide 7.1. Renison, Australia
C þ CO2 ! 2CO Cassiterite in Renison Bell mine is mainly associated with pyr-
rhotite, quartz, dolomite, siderite, and dorite. Beniuk et al. (1994)
SnO2 þ CO ! SnO þ CO2 discussed the process improvements in the gravity concentration
circuit. In addition, the research paper highlights beneficiation
Stannous oxide reaction with sulphide
practice and first installation of the Kelsey centrifugal jig. Fig. 12
SnO þ FeS ! FeO þ SnS shows the gravity concentration flowsheet at Renison concentra-
tor, Australia (Beniuk et al., 1994). The requirement of incorporat-
Stannous sulphide is driven off as a vapour at 1250 °C and
ing Kelsey jig in the plant was to improve the plant efficiency and
passed through freeboard of the kiln. Oxygen is introduced into
operating economics as well as to reduce the environmental pollu-
the kiln. Stannous sulphide is oxidised back to stannic oxide
tion by closing the acid leaching plant. It is reported that the Kelsey
(SnO2), which is in the form of a fume. Later, SnO2 is collected after
jig was able to handle particle size 40 + 5 lm. The finer particle
gas cooling in the kiln by means of a baghouse fabric filter.
separation was possible due to the centrifugal force applied in
SnS þ 2O2 ! SnO2 þ SO2 addition to the gravitational force. The gravity circuit produces
plant’s majority of the tin concentrate. The Kelsey jig design limi-
The sulphur dioxide removed from the gas stream using a lime
tations and subsequent important modifications in the plant envi-
scrubber, wherein, calcium sulphate is formed for the safe disposal.
ronment are summarized in this article.
SO2 þ CaO ! CaSO3 The plant performance after installing J650 model Kelsey jig in
the gravity concentrate and tailing streams are presented in
CaSO3 þ O2 ! 2CaSO4 Table 8.
This article provides an overview of the plant commissioning of
J650 model Kelsey jig along with its’ operational difficulties and
7. Beneficiation flowsheets and plant practices subsequent modifications in screen aperture, mechanical arrange-
ments, etc., that led to the development of a new industrial jig. The
The tin processing flowsheets are somewhat complex as it studies show that the performance of Kelsey centrifugal jig was
involves controlled comminution, and multi-stage concentration better than conventional shaking tables in terms of product grade
for coarse, fine, and ultra-fine particles. Most of the tin produced and recovery.
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 lowed by sulfide and tin flotation units. Each of the sulfide and
concentrator. The gravity concentration plant was recovering 45– tin flotation banks consists of rougher, scavenger and cleaner units.
50% tin. Later, flotation circuit was developed and incorporated Primarily, sulfides are removed from the gravity tailings using cop-
along with the gravity circuit to enhance the tin recovery values. per sulfate as a depressant, xanthate as a collector, and cresylic
Fig. 13 shows flotation circuit consisting of desliming units fol- 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%
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).
The need for further improvement of the concentrate grade reveals that the multi-gravity separator could recover most of
arose due to collapse in tin price during October 1985. Following the tin values located in 45 + 12 lm size fraction. Whereas, flota-
attempts were made to improve the concentrate grade tion column fails to recover particles in that class as a result recov-
ery of tin was low.
– Increasing conditioning time of rougher concentrates.
– Reducing entrainment of low-grade slimes by increasing the 7.3. Rooiberg and Union Tin Mine, South Africa
froth depth.
– Introduction of flotation column (0.76 m diameter, 9.75 m Falcon (1985) compiled history of tin, occurrence, operations,
long). processing flowsheets and their developments took place in the
– Replacing the process water by fresh water in column and clea- South African continent. Tin in South Africa mainly occurs in
ner cells, etc. hard-rock deposits of Rooiberg, Union Tin and Zaaiplaats regions
with operating underground mines. Brief tin mining activities in
Consequently the concentrate grade has improved to 50.70% Sn many mines of these regions are covered in the article. Typical
with 63.31% stage recovery. tin beneficiation flowsheet operated at Rooiberg tin mine is shown
Further, laboratory investigations carried out at Camborne in Fig. 15. The other mines are having more or less similar benefi-
School of Mines revealed that the grade/recovery benefits can be ciation schemes with few variations as per the nature of the raw
achieved by incorporating multi-gravity separator in place of flota- material. The Cornish engineers were initially designed and oper-
tion column. The influence of operating variables such as feed pulp ated Rooiberg mine. The plant was having a capacity to treat
density, drum speed, throughput, wash water rate, angle of tilt and 20,000 tonnes of ore per month with the tin content varying
shaking intensity on the performance of MGS was discussed in between 0.5% and 0.7%. The run of mine was crushed, screened
detail. Summary of plant test results of mine scale MGS is shown and fed coarse product (12 + 1 mm) to a 310 mm Dynawhirlpool
in Table 11. gravity separator, wherein, separating density of 2.9 was main-
The table clearly reveals the improvement in grade and recov- tained using 100 D ferrosilicon medium. The fines fraction was
ery by MGS over a flotation column. The economic gains are related subjected to a 125 mm DSM (Dutch State Mines) cyclone, which
with the cheaper operating costs of MGS over the flotation column. was operated with 100 D ferrosilicon and magnetite mixture. The
Detailed investigations on higher performance of MGS over the flo- concentrates from the heavy medium separators contain 2–3%
tation column are presented through Tables 12 and 13. tin was further processed through milling and tabling circuit to
Size analysis and size-wise Sn distribution of concentrate and upgrade the tin values to 12–20%. The milling and tabling circuit
tailing samples collected from the flotation column and multi- consists of stage grinding by rod and ball mills with intermediate
gravity separator units are presented in the above tables. The tin gravity recovery tables. The pre-concentrate was further subjected
content is mostly distributed in coarse particle size range to dressing section, which was similar to mill-table circuit in addi-
(45 + 12 lm), recovery of each size fraction to the concentrate 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-
Table 11 ity units, hence a lot of fine tin (43 lm) was rejected into the tail-
Comparison of flotation column and MGS performance (Turner and Hallewell, 1993). ings. The Union Tin Mines commissioned South Africa’s first
cassiterite flotation circuit during 1971 and tested many reagents
Sn (%) Flotation circuit recovery of Sn (%)
to recover the tin oxide mineral. The most promising reagents
Feed Tail Concentrate
investigated were iso-hexyl phosphonic acid with sodium oleate,
MGS 0.600 0.209 55.42 65.41 dialkyl sulphosuccinamate, ethyl phenyl phosphonic acid (EPPA),
Column 0.575 0.227 50.16 60.79
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
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 San Rafael plant was treating the ore assaying 2–5% Sn. The ore
(depressant), wherein slurry pH of 4.5 was maintained. Flotation was coarse grained and part of the concentrate was produced in
circuit was designed at Rooiberg in 1972, following previous expe- coarse size (8 mm). Cassiterite is the tin bearing mineral in the
rience at Union Tin mine to treat current tailings and slimes ore, which is associated with silicates, pyrites, pyrrhotite, tourma-
reclaimed from the tailing dams. The flotation plant performance line, copper and silver in small quantities. The gravity concentra-
at Union and Rooiberg plants on old tailings are presented in tion circuit mainly consists of jigs, spirals and tables that
Table 15. 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
7.4. Huanuni concentrator, Bolivia (Fig. 17). It consists of desliming cyclones followed by sulfide and
tin flotation cells. The final tin concentrate after three stages of
Cassiterite is the main tin mineral along with minor quantities cleaning enrich SnO2 content to 36%, later, it is subjected to the
of stannite in Huanuni deposit, Bolivia (Bulatovic, 2010). The gan- multi-gravity separator for further enrichment. The operating con-
gue minerals present in the ore are quartz, pyrite, marcasite, pyr- ditions of the flotation plant are presented in Table 16.
rhotite, and arsenopyrite. Most of the tin is liberated in the Ruiz et al. (2004) presented improvements in the grade and
coarse size fraction (400–300 microns), and some portion is liber- recovery after installation of a pilot-scale jig (GEKKO IPJ 2400) in
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
Fig. 18. Coarse cassiterite recovery circuit at San Rafael, Peru (Ruiz et al., 2004).
7.6. Tin-Tungsten multi-mineral ore, Kyrgyzstan, Central Asia (Angadi, 2012; Jeon et al., 2013). Hence developed flowsheet
shown in Fig. 21 enriches the tin content in the final concentrate
Srinivas et al. (2000) and Sreenivas et al. (2004) reported the to 48–49% with overall recovery of about 92%.
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). 8. Conclusions
The primary gravity concentrate collected from the mine site
assays about 18.05% WO3 and 38.11% SnO2. Both tungsten minerals The beneficiation of cassiterite is an age-old technique that has
wolframite and scheelite occurs in liberated state as well as fine undergone many changes over time. The commercial demand for
distribution in each other. Cassiterite also found in liberated as tin fluctuates with respect to its area of applications. During the
well as intergrowth of columbite/tantalite and has fine dissemina- 1950s, demand for metal was mainly from the tin plate industries,
tion of tungsten minerals within it. Because of this complex asso- while in recent times more demand is reported from the electronic
ciation of minerals an integrated process has been developed, and soldering industries. Cassiterite is the prime economic tin min-
which consists of physical beneficiation and chemical extraction eral that occurs in alluvial and hard-rock deposits. The existing lit-
techniques. The physical beneficiation route tested is shown in erature on cassiterite beneficiation is mainly focused on gravity
Fig. 19. The specific gravity, magnetic and electrical conductivity concentration and flotation techniques. In addition, a few pub-
of wolframite, scheelite and cassiterite were explored in the sepa- lished articles discuss the ultra-fine particle processing techniques
ration. The concentrate thus generated was purified following the such as selective flocculation, shear flocculation and spherical
chemical route depicted in Fig. 20. Tungsten extraction was carried agglomeration.
out by a soda ash roast-aqueous leaching method. This method Many gravity concentrators have been used in the cassiterite
recovers about 90% tungsten values and 8–10% loss in residue. beneficiation to treat coarse (jigs, heavy medium baths/cyclones),
The residue contains 40% SnO2 values that will be mixed with intermediate (spirals and shaking tables), and fine (advanced grav-
the cassiterite gravity concentrate to improve overall recovery val- ity concentrators) particles. Processing of cassiterite fines was one
ues. The combined concentrate assays 67% SnO2 that was further of the driving forces for the development of advanced gravity sep-
processed either by smelting-refining route or roasting-smelting- arators. The efficacy of advanced gravity concentrators such as the
refining route. The proposed integrated flowsheet would recover Kelsey jig, Bartles Mozley separator and Mozley multi-gravity sep-
80–90% tungsten and tin values. arator for treating ultrafine particles has been tested in the pilot-
plant and plant environments.
7.7. Uljin deposit, South Korea A considerable number of research articles have been published
about new surfactants, their chemical aspects, surfactant func-
Tin occurs in Uljin mine in a hard-rock deposit along with peg- tional groups, complex formation with the cassiterite surface, etc.
matite host rocks (Moon et al., 1996). The feed sample analyse 6.4% The widely reported surfactants in cassiterite flotation are cupfer-
Sn, 59.0% SiO2, 13.4% Al2O3, 5.2% Fe2O3 contents. Characterisation ron, arsonic acid, phosphonic acid, fatty acids, salicyaldehyde, sulfo
studies revealed that the tin bearing mineral in the ore is cassiter- succinamate, hydroxamic acids, etc. Most of these surfactants
ite, which occurs in association with quartz, albite, biotite, horn- adsorb on the cassiterite mineral by physisorption and some with
blend, and chlorites. Experiments were carried out on various other specific forces. Many of these collectors are efficient to
gravity concentrators and flotation cells to upgrade the Sn values. recover particle size –38 + 6 lm. The flotation efficiency decreases
Coarse fraction was processed through mineral jig, spiral concen- for >38 lm and <6 lm particle sizes. Unfortunately, several plants
trator and shaking table, whereas, fines fraction was processed are losing cassiterite values in the ultrafine sizes. This requires a
using shaking table and flotation cells. Investigation results show great deal of future study in order to develop tailor-made surfac-
that the coarse circuit (+0.71 mm) could enrich Sn content to 50% tants to float ultrafine particles.
with 53–54% recovery values (Jeon et al., 2011, 2012). The fines cir- Development of advanced gravity concentrators and suitable
cuit consists of shaking tables, ball mill and flotation cells to treat surfactants to recover tin values from ultrafine particle size is the
0.71 mm fines and coarse circuit tails. The fines circuit could subject of considerable interest. For sustainable utilization of nat-
enrich Sn content to 47% with additional 39% tin recovery ural resources and to meet the growing demand it is essential to
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.
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 Angadi, S.I., 2012, Development of process flowsheet for tin ore collected from Uljin
deposit, South Korea. Internal Report submitted to Korea Institute of
and ultrafine tailings.
Geosciences and Mineral Resources (KIGAM), South Korea.
Arbiter, N., 1968, Beneficiation of Cassiterite Ores by Froth Flotation, British Patent
Acknowledgements No. 110643.
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Pez, Bolivia.
The first author would like to acknowledge the Indo-US Science Arslan, F., Giray, K., Önal, G., Gürkan, V., 2002. Development of a flowsheet for
and Technology Forum (IUSSTF) for granting Indo-US Research Fel- recovering copper and tin from copper refining slags. Europ. J. Min. Process.
Environ. Protect. 2 (2), 94–102 (1303-0868).
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What is cassiterite used for?

What is cassiterite used for?

What are the main techniques used to process cassiterite?

What are the main techniques used to process cassiterite?

Minerals Engineering 70 (2015) 178–200

Contents lists available at ScienceDirect

A review of cassiterite beneﬁciation fundamentals and plant practices

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

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

2. Resources, production and consumption 350

Production '000 tonnes

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

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

Physical and chemical properties Details

In stratiﬁcation devices, separation of particles is imparted due

(A) Stratification devices: (a) Jig

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

(E) Miscellaneous devices: (k)centrifugal separators

Fig. 2. Working range of gravity concentration equipments.

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

6. Flotation and ﬁne particle processing

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

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

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

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

6.2.6. Miscellaneous reagents and methods

particles (Sivamohan, 1990). Reduction in ﬂotation efﬁciency is

6.5. Recovery from tailings

Tin recovery from old tailing dumps is gaining wide importance

Tailing projects Reserves (million tonnes) Assay (%) Webpage references

7.2. Wheal Jane, UK

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

Reagent Sulphide circuit Tin circuit

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

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

7.5. San Rafael, Minsur, Peru

Reagent Sulphide circuit Tin circuit

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