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To cite this article: Mineral Processing and Extractive Metallurgy Review (2013): Recycling Process Water in Complex Sulphide
Ore Flotation: Effect of Calcium and Sulphate on Sulphide Minerals Recovery, Mineral Processing and Extractive Metallurgy
Review: An International Journal, DOI: 10.1080/08827508.2013.868346
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F. Ikumapayi etal.,
Recycling process water in complex sulphide ore flotation
Recycling process water in complex sulphide ore flotation: Effect of calcium and
sulphate on sulphide minerals recovery
Abstract
The influence of major components of calcium and sulphate ions in process water on
xanthate collector adsorption and flotation response of pure chalcopyrite, galena and
and XPS spectroscopy studies, while bench scale flotation tests were also carried out
Marginally lower recoveries of chalcopyrite and galena in process water and in the
presence of calcium and sulphate ions in both deionised and process waters using
potassium amyl xanthate as collector were observed in Hallimond tube flotation, whereas
collector. Zeta-potential results show the adsorption of calcium ions on the minerals.
FTIR and XPS studies revealed the presence of surface oxidised sulfoxy species and
surface calcium carbonates and/or calcium sulphate on chalcopyrite and galena in the
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presence of process water and water containing calcium ions at flotation pH 10.5, and
these surface species influenced xanthate adsorption. Surface oxidised sulfoxy and
carbonate species were seen on sphalerite surface in the presence of deionised water,
process water and water containing calcium and sulphate ions at pH 11.5, but the surface
species does not influence xanthate adsorption. Bench scale flotation using two different
complex sulphide ores showed that chalcopyrite, galena and sphalerite recoveries are
higher in process water than tap water and general decrease of the minerals floatability at
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FTIR; XPS.
INTRODUCTION
The production of sphalerite concentrate at Broken Hill, Australia in 1905 was the first
major commercial application of froth flotation which thereafter spread to the rest of the
world and remain the essential step in beneficiation of minerals. The field of flotation
remains quite active and rapidly changing ever since (Fuerstenau et al. 2007b) and
(Fuerstenau et al. 2007a) and the process consumes billions of liters of water. One of the
ways of reducing both plant-operating costs and industrial impact onto the local
ecosystem is to recycle process water through the ore processing plant (Broman 1980;
Rao and Finch 1989; Rao et al. 2010). Such waters, named acid mine drainage (AMD), if
discharged from sulphide flotation contains calcium and sulphate as major species and
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hence, is gypsum (CaSO4.2H2O) – saturated and have a high salinity (on the order of
1000 ppm). As minor species, they commonly contain reduced sulphur compounds
(RSC) (sulfoxyanions with sulphur in the oxidation state below VI), cations of ferrous
and non-ferrous metals, frothing molecules, residual chemical reagents and products of
heterotrophic microorganisms (Garcia et al. 1996; 2005) which play an important role in
dictating their aqueous and solid phase chemical speciation. Consequently, the key step
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of how, in what extent, and why the AMD components, taken singly or together,
In practice, the usual procedure in the flotation stage of complex sulphide ore is floating
Cu and Pb minerals in the first stage while Zn mineral is floated in the second stage
factors which includes components and species present in the pulp (Chen et al. 2009;
Peng and Grano 2010), grinding method (Forssberg et al. 1993) etc. Calcium and
sulphate ions are two very common components in the process water from flotation of
sulphide minerals. Calcium mostly originates from lime used for maintaining pH while
sulphate comes from the ore and other flotation reagents such as NaHSO3 for controlling
Identifying specific effects of recycled water on quality of flotation has been a difficult
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detrimental in some studies where accumulation of species such as calcium, sulphate,
carbonate, rest reagents and their oxidation products, thiosalts and other metal ions leads
to reduced flotation grade and recoveries (Broman 1980; Rao and Finch 1989), while in
other studies they appear to be beneficial to the flotation process (Basilio et al. 1996;
Chen et al. 2009; Liu et al. 1993). Generally the presence of flotation effluents in process
water has been implicated to degrade flotation process however no explicit experimental
evidence for this assertion is yet available. Most previous studies dealt with the effect of
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inorganic anions and metal cations on wide band-gap metal hydroxides (Stumm 1987).
The results have been interpreted in terms of competitive where adsorption of sulphate on
metal oxide increases with sulphate ions concentration (Lefèvre and Fédoroff 2006; Wu
et al. 2002), promotive where the presence of sulphate and calcium ions enhances the
adsorption of arsenate, copper and zinc ions on ferrihydrite (Jia and Demopoulos 2005;
Ostergren et al. 2000; Swedlund and Webster 2001); or indifferent (Lefèvre and Fédoroff
2006) adsorption, depending on speciation of the adsorbed anion and the formation of
Previous attempts on reuse of process water were reported in a number of sulphide ore
concentrators: In Sweden the use of recycled water from settling pond in Kristineberg
concentrator gave rise to significant problems during pumping of the froth which is
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tailings pond (Forssberg et al. 1995). Water reuse in grinding and flotation circuits at
pyrite flotation but selectivity against zinc is adversely affected in flotation of copper and
zinc when sulphate ions concentrations in the water is more than 100 mg/l. In Laisvall
concentrator deterioration of lead flotation and over frothing was experienced due to
precipitation of calcium carbonate in pipes and spray nozzles, the carbonate came from
the mine water. Reuse of water in Zinkgruvan concentrator was stopped due to reduction
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in lead recovery and increase of zinc concentration in lead concentrate, the sulphate ions
concentration in the recycled process water was between 180 and 330 mg/l. Reuse in
Falun concentrator was limited to 25% due to blockage of pipes by gypsum precipitate
which results from saturation of calcium sulphate solution in the tailings pond water, the
sulphate ions concentration in the tailings pond water was 1580 mg/l (Broman 1980). In
Australia, batch flotation study conducted on copper tailings from Benambra mines in
Victoria indicated lower recovery, grade and flotation kinetics when Melbourne process
water was used (Haran et al. 1996). In Canada the use of Kidd Creek process water
containing 500 mg/l thiosalt and 300 mg/l calcium concentration for batch flotation of
Cu-Zn ore from Kidd Creek was not detrimental to copper rougher flotation, it appears to
improve the flotation by enhancing the depression of pyrite and recovery of copper due to
the presence of thiosalt and calcium ions (Liu et al. 1993). In China a lab scale flotation
test on galena and pyrite from Fankou mine using process water collected directly from
the mine concentrator indicated that rest collector in process water from lead flotation
circuit concentrate is beneficial to lead flotation (Chen et al. 2009). In Zambia, the use of
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copper recovery and increases copper loss to tailings due to reduced pH, the deleterious
effect was however removed by addition of quicklime in the primary ball mill (Ng’andu
2001).
It was also reported that froth stability (and viscosity) was higher in the presence of
multivariate metal ions, at concentrations ranging between 15 and 40 mg/l CaCl2 and
AlCl3 due to bridging effect of polyvalent metal ions between the ore particles
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(Farrokhpay and Zanin 2011). Liu and Zhang (2000) demonstrated that calcium ions
Calcium ions adsorbed preferably on chalcopyrite surfaces but not on galena in the
galena at alkaline pH (Liu and Zhang 2000). Contrarily the interaction of calcium species
with fine galena particles was reported to cause depression of galena at increased pulp
conditioning temperature and the condition was improved after addition of soda ash to
the grind such that the pH after grinding was above 10 (Cullinan et al. 1999; Cullinan
1999). Calcium ions could also activate and increase the adsorption of ethyl xanthate on
copper and nickel sulphides after grinding in steel mill when the galvanic interaction
between sulphide particles and the mill iron was effective. The galvanic interaction effect
was indicated by high pulp potential (Kirjavainen et al. 2002). In this study the influence
of process water components; Ca2+ and SO42- were investigated independently and
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practice. Flotation recovery of sulphide minerals at different temperature was also
investigated.
2. EXPERIMENTAL
The pure minerals used in this study were procured from Gregory, Bottley & Lloyd Ltd.,
United Kingdom, and their chemical composition is shown in Table 1. The minerals were
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crushed, ground, classified into different size fractions and stored in sealed polyethylene
bags. A size fraction of −150+38 μm was used in the Hallimond tube flotation tests and
−5 µm size fraction was used in zeta-potential measurement, FTIR and XPS studies. Two
used in the Bench-scale flotation tests. The ores were crushed and wet ground in a steel
mill to obtain K80 ≤ 65 μm size particles, which is the same feed size in plant flotation
operation.
All chemicals used are technical grade. The flotation reagents being used at Boliden
concentrator for treating complex sulphide ores have been obtained. Potassium amyl
xanthate (KAX), Isobutyl xanthate (IBX) and Danafloat 871 (dialkyl dithiophosphate
methanol) was used as frother, dextrin (Boulton et al. 2001; López et al. 2004), sodium
hydrogen sulphite (NaHSO3) (Khmeleva et al. 2003), and zinc sulphate (ZnSO4) (Cao
and Liu 2006) were used as pyrite and sphalerite depressants in flotation. Calcium oxide
(CaO), HCl and NaOH solutions were used as pH regulators and K2SO4 and CaCl2 as
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sources of SO42- and Ca2+ ions respectively. Process water containing 128 mg/l Ca2+ and
63 mg/l SO42- ions, and 186 mg/l Ca2+ and 153 mg/l SO42- ions concentrations were
the water was the filtrate from filtration of zinc concentrate product after flotation (the
flotation was preceded by copper and lead flotation). An analysis of Boliden process
water for chemical species showed that calcium, sulphate and iron are the major species
(Table 2).
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The Hallimond flotation tests were conducted with 1 g of mineral sample conditioned in a
100 ml standard volumetric flask and subsequently transferred into a 100 ml Hallimond
tube flotation cell. This was followed by flotation under magnetic stirring. The sequence
frother. Conditioning time for species in water, collector and frother were 10 min, 5 min
and 1 min respectively. Air was supplied at the rate of 0.2 dm3/min and the flotation time
was 1 min. A collector concentration of 20 mg/l and a frother dosage of 50 µg/l were
used. All tests were carried out at pH 10.5 for chalcopyrite and galena and 11.5 for
Zeta potential measurements were carried out with the aid of ZetaCompact instrument
equipped with a charge-coupled device (CCD) video camera and Zeta4 software. The
software allows the direct reading of zeta-potential calculated from the electrophoretic
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mobilites using Smoluchowski equation. The result is a particle distribution histogram,
of solution was used. The ionic strength was maintained with KNO3 at a concentration of
0.01M and the pH was adjusted with solutions of HNO3 and KOH accordingly. The
required concentration of each solution was usually prepared followed by addition of the
mineral, conditioning for 10 minutes and addition of other required reagent and species.
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always regarded as the pH of the measurement. All the measurements were carried out at
the flotation pH 10.5 for chalcopyrite and galena and 11.5 for sphalerite unless stated
otherwise.
The instrument used was Bruker FTIR spectrometer model IFS 66v/s. The samples were
prepared similarly as in zeta-potential and the pulp is subsequently filtered and left to dry
on the filter paper at room temperature. The pH of the suspension after all conditioning
infrared Fourier transform (DRIFT) method was used in the measurement with 2.8 wt%
concentration in potassium bromide (KBr) matrix. Each spectrum was recorded after 256
scans.
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2.5 XPS Measurements
The samples subjected to XPS measurement were prepared the same way as the FTIR
samples and were used as dry sample during the analysis. The measurement was carried
out with the aid of a Kratos Axis Ultra electron spectrometer using mono AlKα operated
at 150W X-ray source and a low-energy electron flood gun for charge compensation. The
volatile components in the sample such as water and elemental sulphur. The procedure
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involves the pre-cooling the end of sample transfer rod at -170oC for 20 minutes and
pumping of the introducing chamber to 5x10-5 Pa. The sample was subsequently
transferred and kept in the pre-cooled manipulator until base vacuum of 6x10-7 Pa was
reached. The scale of the binding energy (BE) was referenced to C1s line of aliphatic
carbon contamination, set at 285.0 eV. Processing of the spectra was done with Kratos
software. The S2p spectra were fitted with symmetric peaks using S2p3/2-S2p1/2 doublets.
The measurement procedure and data acquisition was as described by Sandström et al.
(2005).
treatment of complex sulphide ores. In each test 1 Kg of ore (received already crushed to
-3 mm) is wet ground with 600 ml of tap water or process water in a stainless steel mill
of 2.5 litre capacity. The sequences of reagent additions were pH regulator, depressants,
collectors, frother, and flotation. The dosages of depressants are; 1500 g/t ZnSO4, 300 g/t
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NaHSO3 and 200 g/t of dextrin. Dosages of collectors in a three stage sequential copper-
lead flotation are 30+20+10 g/t Danafloat and 10+5+0 g/t KAX. The conditioning times
for pH regulator, depressants, and collectors are 5 min, 1 min and 2+1+1 min
respectively. Dosages of zinc activator and collector in a three stage sequential flotation
were 400 g/t CuSO4 and 40+20+20 g/t IBX. The conditioning times for zinc activator and
collector are 2 min and 1+1+1 min respectively. The frother dosage was 20 g/t Dowfroth
in all cases; pH was regulated with powdered calcium oxide. Experiments were
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performed at room temperature of approximately 22oC and at 11°C and 4°C. Total
flotation time was 4.5 min (1+1.5+2) in each successive stage. The three float products in
each test are combined for the chemical analysis and the tailings water (water after
flotation) was assessed for Ca2+ and SO42- ions. The initial concentrations of Ca2+ and
SO42- ions in pulp solution were calculated based on reagents addition such as NaHSO3,
ZnSO4, CaO and CuSO4 while the final concentrations were analysed in the liquid
separated from tailings after zinc flotation. For temperature variation tests, a specially
constructed hollow wall stainless steel flotation cell of 2.5 litre capacity was used and the
pulp temperature is controlled by pumping chilled glycol through the hollow wall of the
cell. All flotation products and the pulp liquids have been analysed at Boliden research
and development laboratories: Atomic absorption spectroscopy (AAS) was used for
analysis of calcium and low concentration of copper, lead and iron while inductively
coupled plasma mass spectrometry (ICP-MS) was used to analyse high concentrations of
copper, lead and iron. Zinc was analysed by titration with ethylenediaminetetra acetic
acid (EDTA) solution (the zinc solution titrated was obtained after dissolving the sample
in nitric acid (HNO3) in combination with other classified solutions). Total sulphur was
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analysed using Leco sulphur analyser. Sulphate was analysed by spectroscopic evaluation
of barium sulphate (BaSO4) turbidity obtained after mixing the sample with barium
All experiments are repeated three times and the mean of three data are recorded. The
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reproducibility of the results is within ±5% error. The flotation results of the minerals as a
again, while for galena it decreases from pH 3 to pH 6 above which it rises. However the
flotation between pH 7 and 9 is the same around 50%. Sphalerite recovery decreases
sharply from pH 3 and remains averagely constant above this pH value. Minerals
recoveries are generally lower in process water except at pHs 3 and 11.5 for sphalerite
and galena respectively. Flotation response of sphalerite is only marginal at all basic pH
values showing that the collector is not adsorbed; it is clear that the collector is not
adsorbed even in process water containing various metal ions such as Cu2+ (Chandra and
Gerson 2009), Fe2+ (Zhang et al. 1992) and Cd2+ (Ralston and Healy 1980) that could
and process water for chalcopyrite and galena at pH 10.5 and sphalerite at pH 11.5 is
shown in Fig. 2. The presence of Ca2+ ions in deionised water decreases the flotation of
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chalcopyrite on the average and more evidently between 50 and 100 mg/l calcium
deionised water; however there is a little increase in process water on addition of 50 mg/l
to 400 mg/l Ca and a sharp decrease after addition of 500 mg/l. A sudden drop in
recovery of galena at 500 mg/l of calcium ions addition is thought to be due to adsorption
of precipitated calcium carbonate on the mineral surface making the surface more
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hydrophilic. Presence of SO42- ions in deionised water decrease the flotation of galena on
the average (Fig. 3). It was suggested that the strongly bonded SO42- ions on the mineral
surfaces inhibits collector adsorption (Ikumapayi et al. 2012a). Two high recovery points
seen on addition of 400 and 1600 mg/l sulphate addition could not be completely
explained scientifically in this work, however it could be suggested that the sulphate ions
are more in solution and not bonding directly on the mineral surface until after 400 mg/l
concentration in solution. While the ionic strength effect at 1600 mg/l sulphate
Calcium ions in deionised water relatively decrease the flotation of sphalerite a little up to
200 mg/l after which the recovery remains constant, a gradual decrease can also be seen
in process water up to 600 mg/l calcium concentration, above which the recovery is
restored to initial level (Fig. 2). In general the recoveries are a little more in process water
than in deionised water. This was suggested to be due to the presence of cationic species
in the process water that could activates sphalerite such as copper ions, lead ions and rest
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reagents Similar results can also be seen with SO42- ions (Fig. 3). The flotation results
show only partial recovery of sphalerite and for its flotation the necessity of copper ions
2012b).
The reduction in floatability of chalcopyrite and galena in the presence of calcium was
due to formation of CaCO3 between calcium and carbon dioxide dissolved in the pulp on
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the surface of the mineral particles and/or CaSO4 which inhibits collector adsorption as
seen under FTIR and XPS studies. For example carbonate formation on chalcopyrite
surface in the presence of 5x10-4M xanthate is evident in FTIR absorbance bands (around
1448 cm-1 and 876 cm-1 wave numbers) in process water and also with addition of 300
mg/l of calcium ions in deionized water (Fig. 12). The XPS results in Table 3 showed the
presence of calcium atom and carbonate species on the mineral surface at 348.3 eV and
290 eV binding energies respectively. In the presence of SO42- ions, the strongly bonded
SO42- ions on the mineral surfaces inhibit collector adsorption (Wu et al. 2002; Lefèvre
and Fédoroff 2006). The recovery in process water is generally lower than in deionized
water probably due to the adsorption of sulfoxy species that exist in process water.
Process water components including SO42-, SO32- (Houot and Duhamet 1992), dissolved
iron (Kant et al. 1994; Peng et al. 2003a), copper (Fullston et al. 1999) and iron hydroxyl
species adsorption form hydrophilic layers on the surface of chalcopyrite; thus inhibits
collector adsorption to some degree as confirmed under XPS studies. Sphalerite recovery
looks better in process water than in deionised water due to the presence of species in the
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The variation in the minerals floatability at increasing pH could also be explained by the
degree of mineral surfaces oxidation i.e. hydrophilic metal hydroxides sites on the
minerals inhibits their self-induced floatability and depending on the metal the effect of
chalcopyrite is high at mildly acidic and alkaline pH while presence of metal hydroxide
surface not coated by hydroxide and xanthate also interact with the metal hydroxide by
ion-exchange thereby reducing the hydrophilic area at the surface. The interaction effect
of xanthate on surface metal hydroxide however depends on the metal e.g. xanthate
interaction with metal in lead hydroxide is more effective than in zinc hydroxide. The
surfaces while the presence of hydroxide species at alkaline pH relatively lower their
floatability (Senior and Trahar 1991). Similar but not exact floatability of galena and
sphalerite was reported by Trahar et al. (1994) whereby natural floatability was higher in
the order of chalcopyrite, galena and least in sphalerite at pH 8. It should be noted that
the minerals samples used in the referenced work were handpicked samples purer than
the ones used in this work. The samples in this work are highly oxidized and were used as
received due to the aim of this study. The level of oxidation of the minerals used was
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3.2 Zeta-Potential Studies
are shown in Fig. 4. The mineral surfaces are negatively charged in the entire pH 3 to 12
region either in deionised or process water, and an extrapolation of the curves shows an
iso-electric points (iep) similar to ieps that have been documented by several authors
(Healy and Moignard 1976; Vergouw et al. 1998; Fullston et al. 1999). It can be seen that
deionised water except for sphalerite in which the negative charge density is mostly
constant between pH 4 and 10 after which a sharp drop of potential was observed. The
reduction is seen in process water only after pH 8 for galena and sphalerite.
The zeta-potential of chalcopyrite and galena at pH 10.5 increases as the calcium ions
ions for sphalerite at pH 11.5 (Fig. 5) while approximately stable between 0 and 1000
mg/l sulphate ions but averagely rises and stabilises from 1200 to 1600 mg/l (Fig. 6). An
attributed to the presence of CaOH+ species and their adsorption on the surface as
suggested earlier (Ikumapayi et al. 2012b). Presence of 700 mg/l sulphate ions in calcium
solution has no marked influence (Fig. 5) while 300 mg/l calcium ions in sulphate
solution sharply increase the zeta-potential indicating dominant effect of calcium ions on
all the minerals (Fig. 6). The zeta-potential increases (becomes less negative) with
increase in calcium ions concentration due to their adsorption (Moignard et al. 1977).
Since the sulphate ions have no significant effect on adsorption, the increase in zeta-
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potential in the presence of only sulphate in Fig. 6 could be due to the increase in ionic
strength.
In our elaborate work (results not shown here); similar trends of the minerals zeta-
in solution as well as in the presence of the following sulphide mineral flotation reagents:
ZnSO4 a depressant for zinc minerals, NaHSO3 a common depressant for pyrite and
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Generally all zeta-potentials measured in the presence of calcium ions are identical, and
also identical to those measured in process water. The high zeta-potential in process
water and in the presence of calcium ions than in deionised water is due to the presence
of positively charged metal ions in process water which adsorb on the surfaces of the
minerals particles may be enhanced (Zhang et al. 1997; Fuerstenau and Pradip 2005) a
water. Negative surface charge arises due to the sulphide anions, copper and iron cations
interacting with oxygen of hydroxyl species. Overall, the effect of calcium ions is
There could be little discrepancy between the observed and referenced bands due to
instrument calibration, sampling technique and concentration effects. All the spectra are
drawn to the same scale and were deliberately shifted in the figures for the purpose of
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comparison. The FTIR-DRIFT spectra of the minerals treated in deionised and process
water at basic pH 10.5 for chalcopyrite and galena and 11.5 for sphalerite are shown in
Fig. 7. The bands depicting surface sulfoxyanions and oxy-hydroxide species seen in
deionised water at 1169 and 1008 cm-1 can be assigned to S–O stretch vibrations in
The spectra in process water illustrate additional bands in chalcopyrite and galena, a
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broad band at 1450 cm-1 and a sharp band at 879 cm-1, representing C–O stretch and C–O
out-of-plane bend respectively in carbonate structural unit (Persson 1994; Smith 1999;
Socrates 2001). It was clearly shown elsewhere that the species present in process water
are adsorbing on the minerals more significantly on chalcopyrite followed by galena and
The band frequencies related to sulfoxyanion species (1008 cm-1), mainly sulphate and/or
sulphites are the same on chalcopyrite, having similar intensity with increasing calcium
concentration in both deionised water (Fig. 8) and process water (Fig. 9). No obvious
process water, carbonate species bands are seen to increase with increased calcium
seen for chalcopyrite in Fig. 9. Since the solids are collected after filtration, any bulk
calcium carbonate precipitation remain in the solids fraction and hence seen in the
spectra. Since the solubility of calcium sulphate is much higher than calcium carbonate,
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Figs. 10 and 11 show the influence of sulphate concentration on chalcopyrite in deionised
and process waters respectively. The S–O stretching bands at 1008 cm-1 both in deionised
water and in process water are seen to increase with increasing sulphate concentration.
Similar but not exact trend was seen on galena and sphalerite at increasing calcium and
sulphate concentration. Since the intensity of the broad bands at 1450 and 879 cm-1 was
seen to increase with increasing calcium concentration in water they most probably
seen in XPS data presented in Tables 3, 4 and 5. The bands related to sulfoxyanion
species, mainly sulphate and/or sulphites are found to be the same with increasing
calcium concentration. However, the S–O stretching bands (1008 and 1169 cm-1) in
deionised water and in process water (1008, 1050, and 1169 cm-1) are seen to increase
with increasing sulphate concentration but also decreased in process water at 1000 ppm
SO4 concentration probably due to gypsum formation which also dissolve in solution.
There is no significant difference between the bands for sphalerite treated in deionised
water and process water at pH 11.5 (Fig. 7) however the peak at 879 cm-1 seen in both
waters indicates some carbonate contamination present in the sphalerite sample and this
peak was also seen in our elaborate work to increase as calcium concentration is
The spectra of chalcopyrite treated with xanthate in deionised and process waters and in
the presence of calcium and sulphate ions after subtracting the pure mineral spectrum
conditioned in respective waters at the same experimental pH 10.5 without xanthate are
shown in Fig. 12. The xanthate concentration of 5x10-4 M used in deionised water show
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prominent bands associated with adsorbed xanthate species at 1225 and 1148 cm-1. An
additional band at 1022 cm-1 was also observed with the use of 5x10-5 M xanthate. The
higher intensity band 1148 cm-1 can be assigned to C–O–C vibrations and the bands at
1225 and 1022 cm-1 are due to S–C–S and C–O–C stretching vibrations (Leppinen et al.
1989; Leppinen 1990; Persson 1994; Mielczarski et al. 1998; de Donato et al. 1999). The
observed bands 1148 cm-1 and 1225 cm-1 are also characteristic of copper xanthate and
dixanthogen respectively. The bands at 1148 and 1022 cm-1 diminished in the presence of
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calcium while a broad and a sharp band associated with surface carbonate species
emerges at around 1440 and 874 cm-1 respectively indicating reduced adsorption of
xanthate due to the formation of surface carbonate. In process water, the S–O stretching
band at 1050 cm-1 dominates over xanthate species bands, except at higher xanthate
sulphate ions and xanthate show a negative carbonate band at 874 and 1440 cm-1
indicating that the surface carbonate layer is more concentrated when treated in process
water than in the presence of xanthate. This could be due to ion-exchange between
carbonate anions and xanthate or impeded surface calcium carbonate precipitation in the
presence of xanthate.
The difference spectra of galena after treatment in two xanthate concentrations solutions,
5x10-4M and 5x10-5M, and in the presence of calcium and sulphate in deionised and
process water at pH 10.5 are shown in Fig. 13. The xanthate spectra in deionised water
showed three bands associated with adsorbed xanthate components at 1035, 1135 and
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1193 cm-1. The band at 1193 cm-1 is related to the C-O-C and S-C-S asymmetric
stretching vibration band, the 1035 cm-1 band is associated with the asymmetric
stretching vibration of the S-C-S molecule groups while 1135 cm-1 is related to stretching
vibration of the C-O-C groups. These bands are considered monocoordinated and
multilayer forms of surface precipitated lead xanthate (stoichiometric or not) (Cases and
de Donato 1991). The intensity of the bands are lower in process water compared to
In the presence of calcium the intensity of surface lead sulphate and lead carbonate bands
are seen to decrease and the spectra also displayed negative bands. Xanthate adsorption
on galena is also reduced in the presence of calcium as shown by the decreased intensity
of xanthate bands (1193, 1135, and 1035 cm-1). Similar spectra but in process water show
that the surface oxidized compounds, in particular surface carbonate, is absent. In process
water and in the presence of 5x10-5 M xanthate, the spectrum shows very intense
carbonate bands at 1448 and 876 cm-1, which not only disappeared but also show
negative bands at the same region on addition of calcium. The presence of sulphate ions
shows that the surface sulphate and carbonate is marginally removed from the surface in
both deionised and process waters. Xanthate adsorption band is also seen to reduce in the
Calcium ions and sulphate species in process water is seen to form calcium carbonate and
lead sulphate on galena surface more than in deionised water which may inhibit xanthate
collector adsorption leading to lower flotation rate of galena observed in Hallimond tube
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flotation tests. The positive and negative lead sulphate (around 1000 cm-1) and lead
carbonate (around 1400 cm-1) bands (Fig. 13) illustrates different level of surface
spectrum that was subtracted. The successive decrease in surface oxidised compounds
bands in the presence of calcium could be due to a result of surface sulfoxy and
carbonates species forming soluble complexes with the calcium and dissolved into the
Xanthate adsorbs on galena to form mono-coordinate lead amylxanthate (1135, 1035, and
1193 cm-1) both in deionised and process waters, however process water suppressed
xanthate adsorption where xanthate species bands intensities were lower. Upon xanthate
calcium and sulphate ions as shown by the decreasing intensity of xanthate bands (1193
and 1035 cm-1), this is suggesting that calcium in process water may reduce xanthate
adsorption onto galena. The calcium and carbonate observation in XPS at 348 eV and
The spectra of sphalerite treated with xanthate in deionised and process waters and in the
presence of calcium and sulphate ions after subtracting the pure mineral spectrum
conditioned in respective waters at the same experimental pH 11.5 without xanthate are
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shown in Fig. 14. The xanthate concentration of 5x10-4 and 5x10-5 M used in deionised
water show prominent weak vibration bands associated with xanthate species on
sphalerite at 1050, 1078 and 1175 cm-1 (Leppinen 1990; Basilio et al. 1996; Larsson et al.
The surface oxidized products of sphalerite are expected to be removed during the
abstraction of xanthate as seen in the spectrum for 5x10-4 M xanthate in deionised water
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and in the presence of calcium and sulphate in both waters (xanthate can complex with
the metal of the oxidation product as stated earlier thereby dissolving the oxidised species
in solution). The presence of oxidation species in other spectra indicates that the
maximum initial xanthate concentration is not adequate to form monolayer coverage. The
reduced xanthate bands could be as a result of xanthate complex formation with the metal
In process water, the carbonate band (1450 and 877 cm-1) dominates over sulphates and
xanthate species bands, weak intensity bands compared to deionised water. The intensity
of C-O bands was similarly seen to increase with increasing calcium concentration in
bulk solution as seen in XPS Table 5. In both galena and sphalerite the two carbonate
peaks at 1448 cm-1 and 876 cm-1 wave numbers are seen at lower xanthate addition but
not at higher concentration level (Figs. 13 and 14). This could similarly be due to ion
exchange mechanism whereby xanthate at higher addition rate complex with the metal
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3.4 X-Ray Photoelectron Spectroscopy (XPS) Studies
Pure mineral samples used in XPS measurement were prepared similarly as the samples
used in FTIR measurements. Spectra of minerals surface components in this study were
recorded at similar binding energies found in literatures and databases (Chernyshova and
Andreev 1997; Kartio et al. 1997; Laajalehto et al. 1993; Nowak and Laajalehto 2000;
Nowak et al. 2000; Page and Hazell 1989; Pillai et al. 1983; Frost et al. 1977; Szargan
and Karthe 1992). The XPS results of chalcopyrite, galena and sphalerite are summarized
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in Tables 3, 4 and 5 respectively while important results are shown in Figs. 15 and 16.
The tables show the common binding energies and line at which signals corresponding to
different species are observed and the atomic concentration of each element on the
The XPS results of chalcopyrite (Table 3) treated in deionised water show high oxidised
species (Cu-O; Cu-OH) and lower Cu-S on mineral surface compared to the sample
conditioned in process water. In process water, the surface contains in addition CO32- and
Ca species, and relatively lower Cu-O species (Mielczarski et al. 1996a; Mielczarski et al.
1996b). The results of galena (Table 4) show more of oxidised species (CO32-; Pb-O; Pb-
OH) and lower Pb-S in deionised water compared to the samples conditioned in process
water. In process water, relatively high Pb-OH, lower CO32- and significantly low Pb-O
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Calcium, carbonate and sulphate species are seen on chalcopyrite and galena mineral
high while xanthate adsorption is relatively low in process water. Thus the surface
recovery of chalcopyrite and galena observed in process water relative to deionised water
under Hallimond tube flotation is difficult to correlate directly with the surface species.
However bench-scale flotation results (Table 6) corresponds well to the XPS results with
The XPS results of sphalerite (Table 5) treated in both deionised and process water show
that the surface contains equivalent of oxidised (Zn-O; Zn-OH) and sulphide (Zn-S)
species in deionised water. In process water, the surface also contains Ca species, and
relatively high CO32- species. Adsorption of xanthate species in process water is high
relative to in deionised water. Thus the surface calcium carbonate in process water is not
The C 1s and S 2p spectra corresponding to carbon and sulphur atoms present in different
species on chalcopyrite surface are shown in Figs. 15 and 16 respectively. Similar spectra
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for galena and sphalerite are shown elsewhere (Ikumapayi et al. 2012a, Ikumapayi et al.
2012b).
The C 1s level of mineral samples treated in deionised and process water solution of
xanthate shows peaks signifying four chemically in-equivalent carbon atoms on the
minerals surfaces. The peaks are observed at BEs around 285, 286.4, 288.1 and 290 eV
(Fig. 16). The atoms have been identified by different authors as originated from both
hydrocarbon contaminants on the minerals surfaces and species from the xanthate.
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The most intense C 1s peak observed on all mineral samples is around 285 eV and it can
be associated with C-(C,H) species. The peak around 286.4 eV can be associated with C-
O, 288.1 eV with COOH species, while the peak around 290 eV is associated with
carbonate species (CO32-) suggesting the presence of low CaCO3 and/or CuCO3, PbCO3
and ZnCO3 on chalcopyrite, galena and sphalerite samples respectively treated in both
waters (Nowak and Laajalehto 2000) and precipitation of CaCO3 on samples treated in
process water, because of calcium presence in the process water. The peak is more
intense in process water for all the minerals compared to deionised water. The peaks
around 285, 286.7 and 288.7 eV are due to hydrocarbon contamination and substantial
on sulphide mineral with the intensity of 286.7 eV peaks increasing while that of 285 and
288.7 eV decreases in the presence of xanthate (Pillai et al. 1983). High 286.7 eV peak on
chalcopyrite sample treated in deionised water compared to process water was due to a
better adsorption of xanthate on samples treated in deionised water and lower adsorption
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The S 2p lines of chalcopyrite samples treated in xanthate solution (Fig. 16) can be fitted
by three doublets with the position of the S 2p3/2 splitting peaks at about 161.3, 162.1,
164.3 and 169 eV (FWHM 0.65, 1.1, 1.65 and 1.15 eV in deionised water, 0.75, 0.9, 1.4
and 1.15 eV in process water), and S 2p1/2 peaks at about 163.3 and 170 eV. The peaks
around 161.3 and 163.3 eV are characteristic of the chalcopyrite sample and 162.1 eV
was due to the presence of sulphur in xanthate (Mielczarski et al. 1996a; Mielczarski et
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al. 1996b) while 169 eV was suggested to indicate presence of surface sulfoxy specie
such as SO42- due to oxidation of surface sulphur as well as presence of SO42- in solution
(Pillai et al. 1983). Peaks at 164.3 and 170 eV could not be assigned from literature
studies but we suggest that they indicate sulphur in xanthate and sulfoxy species
respectively. The high intensity of the xanthate peaks of samples treated in deionised
The recoveries and grades from bench scale flotation of two types of sulphide ore are
presented in Table 6. Each flotation test was carried out thrice and the data presented in
Table 6 is the average result of the three flotation tests. The reproducibility of the results
is within ±5% error. The two ores used were from Renström and Kritineberg mines;
Renström ore grades 0.36% Cu, 1% Pb and 6% Zn while Kristineberg ore grades 0.9%
Cu, 0.1% Pb and 2.4% Zn. Flotation was carried out using tap and process water at 22, 11
and 4oC temperatures to cover the seasonal temperature changes in process plant from
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winter to spring and summer through autumn in the north of Sweden and with simulated
tap water with added 128 mg/l Ca2+ and 63 mg/l SO42- ions concentration for Renström
ores and 186 mg/l Ca2+ and 153 mg/l SO42- ions concentration for Kristineberg ores as in
respective process water. The recovery of copper mineral from Renström and
Kristineberg ores decreases with temperature while their grade and recovery are higher in
process water than the products in tap water on the average. Lead mineral recovery in
Renström ore is more in process water than tap water and it decreases as temperature
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decreased, while there is no significant change in the grade. Addition of Ca2+ and SO42-
ions singly and combined in the water has little influence on both the recovery and grade
of lead mineral while no clear change is seen in the results of Kristineberg ore besides at
22oC where the recovery is more in process water. There is no significant difference
between recoveries of zinc mineral from Renström and Kristineberg ores using simulated
water and tap water, however the grade is a little more in tap water for Renström ore and
more in simulated water for Kristineberg ore. Process water gives a little more recovery
than tap water for both Renström and Kristineberg ores at 22oC temperature. A little
decrease in recovery of zinc mineral can also be observed at temperature lower than 22oC
for Renström ore in process water compared to tap water while a small but gradual
increase in recovery and grade is observed for Kristineberg ore in process water as
temperature decreases. The relatively low recovery of zinc from Kristineberg ore was due
to ineffective depression of zinc minerals in the ore during copper-lead flotation which
lead to high zinc recovery to copper-lead concentrate observed in our elaborate work
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The floatability of the minerals appears to be generally more in process water compared
to tap water. Addition of Ca2+ and SO42- ions to the water has little influence on the
recovery. One possible reason for better grades in process water is the presence of rest
reagents and high metal ions that enhances collector adsorption on mineral surface as
seen in zeta-potential studies (Chen et al. 2009; Finkelstein 1997). Another reason could
be the reduced oxidised surfaces revealed under DRIFT and XPS studies which could
lead to better efficiency of the little adsorbed xanthate in flotation. The difference in
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flotation response between process and tap water could also be caused by different
grinding environments (Forssberg et al. 1993; Grano 2009; Göktepe and Williams 1995;
Martin et al. 1991; Peng et al. 2003a; Peng et al. 2003b), for example, the pH of process
water is about 11 which is the grinding pH when using process water for flotation as
against tap water in which grinding pH is about 8. The disparity between the flotation
responses in the presence of process water and its components in deionised water
observed in Hallimond tube flotation and the bench scale flotation can also be explained
by the differences in the particle size of the minerals used in Hallimond flotation (-
150+38 µm) and bench scale flotation (K80 ≤ 65 μm). The depressing effects of calcium
and sulphate ions were reported to be more significant on finer particle sizes (Cullinan et
al. 1999; Cullinan 1999). The particle size for the bench scale flotation in this study is the
one used in practice. In order to substantiate the better floatability in process water,
surface of the products and tailings obtained from the flotation tests must be done so that
the surfactant and other species concentration on each product can be comprehended,
these will give indication of what is responsible for the better floatability. The effect of
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particle size distribution must also be tested in order to compare the surface behavior at
different sizes.
Temperature affects water quality through changes in mineral dissolution, gas and metal
hydroxide solubility, solution viscosity, reagent adsorption and stability all of which
temperature decreases cannot be specifically understood, however they are most likely
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for sphalerite, its flotation depends on the amount of copper activation, and it was found
sphalerite surface with increasing copper concentration and temperature. The adsorption
elemental sulphur at the sphalerite surface, which promotes sphalerite flotation (Albrecht
et al. 2010). In addition a study done on the effect of temperature on pyrite flotation
indicates that the rate of flotation is only affected at temperature less than 10oC. This was
due to slow movement of bubbles and high viscosity at the low temperature. The flotation
rate of pyrite decreases with temperature due to reduction in the rate transfer of pyrite
from the pulp to the froth. This is partly because the bubbles rise more slowly at lower
temperatures, and hence higher viscosities. An increase in aeration rate would improve
the flotation rate and infinite-time recovery of pyrite. The use of higher impeller speeds
results in improved flotation rates and recoveries of pyrite without reduction in grade, and
this may overcome the effects of decreased temperatures. Heating of the pulp may also
increase the recoveries, but the economics must be carefully evaluated for each flotation
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plant (O'Connor et al. 1984). Fundamental studies on the effect of temperature on
xanthate adsorption on sulphide minerals will shed more light on the observations from
this study.
The sulphate and calcium species concentration balance in solution for tests on Renström
ore using tap water and process water at 22 oC, 10 oC and 5 oC temperatures are presented
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in Table 7. The concentrations of Ca2+ and SO42- ions prior to the experiment in the tap
water are 22.5 and 7.4 mg/l respectively while in process water are 128 and 63 mg/l
respectively. The initial concentrations shown on the table were calculated after reagents
addition such as NaHSO3, ZnSO4, CaO and CuSO4 while the final concentrations were
analysed in the liquid separated from tailings after zinc flotation. The lower concentration
of calcium in the final flotation solution observed must have adsorbed on the mineral
surfaces and/or precipitated as calcium carbonate as seen in zeta-potential, FTIR and XPS
studies, and the excess of SO42- must have been contributed from the dissolved sulphur
composition of the mineral. Similar but not exact balance was observed with Kristineberg
ore. Depleted calcium ions and excess sulphate ions in the pulp liquid after flotation
precipitation revealed in DRIFT and XPS spectra. The dissolved oxidised surface sulfoxy
species and also the release of sulphate species upon xanthate adsorption contributed to
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4. CONCLUSIONS
The negative zeta-potential of the minerals (chalcopyrite, galena and sphalerite) in the
deionised water than in process water and water containing calcium ions illustrates
adsorption of calcium and other metal cations that exist in process water. This is
subsequently confirmed by DRIFT spectra and XPS of the mineral samples which also
showed further, that the surface is partially oxidised depicting surface sulfoxy and
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Hallimond flotation of chalcopyrite and galena but not bench scale flotation of sulphide
ores. Calcium and sulphate ions hardly have any effect on Hallimond flotation recovery
of sphalerite, however; its recovery is relatively better in process water than deionised
water.
Process water, sulphate and calcium ions suppressed xanthate adsorption on chalcopyrite
and galena where xanthate species bands intensities were lower while they have no effect
water in the presence of xanthate the surface carbonate species bands on the minerals are
by xanthate anions.
bench-scale test of sulphide ore in tap water while the recoveries of the three minerals
increased when process water was used. Sphalerite recoveries were indifferent in tap
liquid after flotation shows decreased calcium and increased sulphate ions indicating that
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there is adsorption of calcium ions on the mineral and dissolution and release of sulphate
ions in solution.
Based on the findings so far the use of process water therefore indicates both detrimental
and beneficial outcomes which are controllable hence can be reused but with frequent
assessment of the components in the water (for example solubility products of calcium
carbonate and sulphate must be monitored in order to know when these components
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could be adsorbing on mineral surface). In addition more detailed systematic studies are
required that addresses other physical and surface characteristics and responses of the
minerals under flotation conditions which should be followed by pilot scale tests before
ACKNOWLEDGEMENTS
The financial support from the Swedish VINNOVA foundation and, Boliden and Lundin
Mining mineral companies for the research project on “Recycling of process water and
acknowledged. Prof. K.H Rao would like to acknowledge the support from the “Centre
Sweden.
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Table 1 Chemical composition of the minerals used in the studies
Minerals % Cu % Fe % Zn % Pb %S
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Table 2 Chemical species and their concentration range in Boliden process water (source;
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Table 3 XPS binding energies and atomic concentrations on chalcopyrite surfaces at different conditions (DW and PW - deionised and process
water)
DW PW DW PW DW PW DW PW DW PW
Line BE, eV pH 10.5 pH10.5 300ppm Ca 300ppm Ca 5.10-5MKAX 5.10-5MKAX 300CaKAX 300CaKAX 1000SO4KAX 1000SO4KAX
C 1s 285.0 14.99 10.74 19.45 9.12 16.2 13.13 15.45 13.26 14.67 14.74 C-(C,H)
286.7 4.6 4.28 4.61 3.43 6.72 3.5 4.31 4.8 2.83 3.25
288.7 0.93 0.91 2.41 1.49 2.02 0.85 1.88 1.53 1.92 1.92 COOH
290.0 4.9 6.47 0.46 5.47 0.79 0.53 CO32-
O 1s 530.4 4.12 2.92 2.48 2.43 2.33 2.01 2.52 2.61 2.8 2.39 Cu-O ?
532.3 51.23 51.75 48.15 51.32 45.18 50.73 45.56 49.02 46.56 47.55 Cu-OH
534.0 2.09 2.25 1.97 1.73 2.73 2.03 2.45 0.84 1.65 1.68 Organic,
K 2p 3/2 292.5 0.21 0.19 0.74 0.57 0.83 0.79 1.05 0.85
293.5 0.88 0.6 0.67 0.57
Cu 2p 3/2 932.6 1.39 1.82 1.79 1.92 3.36 2.05 3.69 3.38 4.21 4.08 Cu(I)
934.7 0.5 0.58 0.52 0.49 0.95 0.47 0.71 1.23 1.09 0.98 Cu(II)?
Fe 2p 3/2 708.0 0.18 0.19 0.31 0.25 0.33 0.14 0.34 0.34 0.43 0.43 CuFeS2
710.5 0.8 0.58 0.67 0.66 0.83 0.69 0.96 0.95 0.8 1.13 Fe(II)?
712.3 8.78 5.46 7.12 6.16 6.57 5.47 8.11 7.91 8.15 7.83 Fe(III)
S 2p 3/2 161.7 1.24 1.37 1.76 1 1.47 1.4 2.23 2.07 2.79 2.16 S2-
162.5 1.56 1.76 1.68 1.96 4.01 1.57 3.66 3.7 3.58 4.71 S22-
163.7 0.66 0.78 0.81 0.79 1.25 1.16 1.66 1.73 2.12 1.78 KAX? poly-S?
165.2 0.44 0.34 0.51 0.48 1.37 0.49 0.67 0.83 1.02 0.85 S(0)?
167.5 0.13 0.16 0.14 0.13 0.22 0.17 0.13 0.18 0.2
169.2 5.02 4.1 4.27 3.32 3.27 3.13 3.13 3.54 3.46 3.46 SO42-
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Ca 2p 3/2 348.3 0.45 4.29 0.71 6.1 4.98 0.97 0.91
99.99 99.99 100.03 100.01 100.01 100.01 100.05 99.97 99.31 99.99
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Table 4 XPS binding energies and atomic concentrations on galena surfaces at different conditions (deionised water, DW; process water, PW)
286.7 10.78 5.07 4.58 4.54 6.38 4.7 5.86 5.97 3.08 4.7
287.9 1.18 1.7 0.94 1.79 1.02 1.29 1.55 1.09 COOH
289.3 8.85 7.26 7.14 8.85 5.78 8.25 6.12 4.88 4.58 4.59 CO32-
O 1s 529.8 25.77 1.77 27.39 1.1 1.07 1.9 0.97 2.7 1.05 1.41 Pb-O ?
531.7 17.17 28.88 15.87 41.7 28.09 36.97 31.12 30.22 32.78 30.09 Pb-OH, SO4, etc
533.0 1.7 12.31 3.17 15.38 4.02 9.37 9.76 9.92 7.9 organic, SiO2
Sb 3d 5/2 531.0 0.58 0.7 0.47 0.7 0.33 0.8 0.75 0.95 0.8 Sb2O5
K 2p 3/2 293.6 0.54 0.56 0.49 0.46 0.58 0.37 0.55 0.44 0.68 0.66
Pb 4f 7/2 137.8 2.27 5.84 6.47 4.67 6.78 5 8.19 7.9 7.43 7.13 PbS
138.3 2.45 9.26 11.37 5.51 10.02 4.77 8.47 8.92 10.04 10.54 Pb(II)
139.2 9.17
140.4 1.75
160.9
S 2p 3/2 162.1 2.22 5.44 5.95 4.18 6.32 4.5 6.89 7.08 6.98 7.33 PbS S2-
163.2 0.84 1.78 1.29 5.51 1.29 0.94 1.71 1.69 1.5 1.98 poly-S? S22- ?
160.9 0.78 0.24 0.39 0.67 0.94 0.84 KAX? poly-S?
1.26 1.38 S(0)?
168.3 0.95 2.38 1.86 1.62 2.25 1.38 1.98 2.64 2.91 2.76 SO42-
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Table 5 XPS binding energies and atomic concentrations on sphalerite surfaces at different conditions (DW and PW - deionised and process
water)
DW PW 300ppm 300ppm DW PW DW PW DW PW
Line BE, eV pH 10.5 pH10.5 Ca Ca 5.10-5MKAX 5.10-5MKAX 300CaKAX 300CaKAX 1000SO4KAX 1000SO4KAX
C 1s 285.0 8.81 12.18 10.61 6.59 15.15 13.18 11.47 16.27 15.11 14.14 C-(C,H)
286.7 3.75 4.3 4.06 2.1 5.41 2.73 4.98 4.53 3.07 3.4 C-O
288.7 1.65 1.43 1.96 1.25 2.45 1.57 2.27 1.93 2.48 1.93 COOH
290.0 1.14 2.59 1.33 8.62 1.2 6.99 1.8 1.88 0.89 1.39 carbonate
O 1s 530.3 6.23 4.87 4.42 2.97 3.99 3.84 4.29 3.62 4.72 3.96 Zn-O ?
Zn-OH, carbonate SO4.
531.5 11.51 7.22 8.56 5.53 9.2 8.45 5.48 8.56 10.85 9.47 etc
532.6 36.36 39.7 38.78 41.04 35.01 39.56 40.02 35.97 34.23 37.28 Organic, SiO2
Si 2p 103.3 8.55
K 2p 3/2 293.8 0.88 0.66 0.71 0.39 0.7 0.57 0.72 0.65 0.84 0.89
Zn 2p 3/2 1022.0 13.65 11.19 12.34 7.11 10.91 7.59 11.67 9.99 11.63 10.86
S 2p 3/2 161.8 14.81 13 13.91 7.57 13.9 8.71 14.63 13.19 13.25 13.31 ZnS
163.1 0.92 1.4 0.54 0.81 1.01 1.09 1.19 1.52 S22-? poly-S ?
168.6 0.94 0.85 0.8 0.67 0.55 0.96 0.66 1.02 0.98 1.08 KAX ?
SO42-
Ca 2p 3/2 348.1 1.1 1.11 7.06 0.72 5.38 1.01 1.3 0.76 0.77
99.73 100.01 99.99 99.99 100 99.53 100.01 100 100 100
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Table 6 Flotation results of complex sulphide ores at pH 10.5 (Cu-Pb flotation) and pH 11.5 (Zn flotation) in tap water and process water. (R and
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Table 7 Calcium and sulphate species ions balance in solution from flotation of
Renström ore at different temperature using both tap water and process water
22 oC
11oC
4oC
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Figure 1 Recovery of sulphide minerals as a function of pH in deionised water (DW) and
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Figure 2 Effect of added calcium ions on flotation in deionised and process water for
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Figure 3 Effect of added sulphate ions on flotation in deionised and process water for
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Figure 4 Zeta-potential of minerals at different pH in deionised water (solid lines) and
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Figure 5 Zeta-potential of minerals as a function of calcium ions concentration (solid
lines) and with a fixed (700 ppm) concentration of sulphate ions (broken lines) at pH
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Figure 6 Zeta-potential of minerals as a function of sulphate ions concentration (solid
lines) and with a fixed (300 ppm) concentration of calcium ions (broken lines) at pH
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Figure 7 FTIR-DRIFT spectra of minerals at flotation pH in deionised (DW) and process
waters (PW).
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Figure 8 Effect of calcium concentration on chalcopyrite at pH 10.5 in deionised water.
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Figure 9 Effect of calcium concentration on chalcopyrite at pH 10.5 in process water.
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Figure 10 Effect of sulphate concentration on chalcopyrite at pH 10.5 in deionised water.
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Figure 11 Effect of sulphate concentration on chalcopyrite at pH 10.5 in process water.
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Figure 12 Difference DRIFT spectra of chalcopyrite treated with 5x10-4M, 5x10-5M
xanthate and 300 ppm calcium and 700 ppm sulphate ions in the presence of 5x10-5M
xanthate after substracting the mineral spectrum treated in deionised water (left) and
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Figure 13 Difference DRIFT spectra of galena treated with 5x10-4M, 5x10-5M xanthate
and calcium and sulphate ions in the presence of 5x10-5M xanthate after subtracting the
mineral spectrum treated in deionised water (left) and similar spectrum in process water
(right) at pH 10.5.
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Figure 14 Difference DRIFT spectra of sphalerite treated with 5x10-4M, 5x10-5M
xanthate and calcium and sulphate ions in the presence of 5x10-5M xanthate after
subtracting the mineral spectrum treated in deionised water (left) and similar spectrum in
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Figure 15 C 1s XPS spectra of chalcopyrite treated in solution containing 5x10-5M KAX
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Figure 16 S 2p XPS spectra of chalcopyrite treated in solution containing 5x10-5M KAX
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