A ELSEVIER fot, Miner Process. 52 (1997) 187-201 Pyrite flotation in the presence of metal ions and sphalerite Q Zhang, Z. Xu, V. Bozkurt, J.A. Finch © Deparment of Mining end Metallica Engineering, McG Unies 340 Unicers Set. Monta (QUA 247 Cana Recsived 5 ul 1996 ace 9 Sly 197 “The effect of Cu", Fe* and Ca°* ions on pyrite Moatability with xanthate as a function of ‘pH in the presence and absence of sphalerite was studied. In the alkaline pH region, these fons activated the pyrite when alone but not when sphalerite was present, Zota-potential measurements and infrared surface characterization confirmed the different interaction with xanthate depending ‘whether the pyrite was alone or with sphalerite. © 1997 Elsevier Science BLY. Keywords: pyrite; spaleite; lation; mineral interaction; metal ions: zeta potentials FTIR 1. Introduction Sulphide mineral ores remain the major source of base metals, The Motation of valuable minerals of copper, lead and zine from pyrite, the main sulphide gangue. has received considerable atention (Forssberg, 1985: Dobby and Rao, 1989). Recently, there has been growing suspicion that metal ions play a role in limiting selectivity of sulphide flotation. These metal ions result from the use of recycle water, the presence of semisoluble minerals and from superficial oxidation of sulphide minerals and steet- srinding media. Their detrimental effect is associated with ether depression of the target ‘minerals or activation of the unwanted mineral (e.g. pyrite) ‘Understanding the role of metal ions is essential for their effects to be countered. In this communication, the action of Cu"*, Fe° and Ca’~ ions on the flotation of pyrite, Coresponding author. Phone: + 1-514-398 4755; Fs +151 sillca 398 4492; E-mail: jim mine a.m: (0301-7516/91/$17.00 © 1997 Elsevier Science BV. All rights reserve, PI $0301 -7516(97}00064-1v8 (0. Zhang era. / ns. Miner. Process, $2 (1987) 187-201, alone or mixed with sphalerite, is reported. Copper ions are routinely used to activate sphalerite, and in some operations are used to activate pyrthotite (Chang et al, 1954; Bushell, 1962; Rao, 1971a.b) and pyrite (Gebhardt and Richardson, 1987). The undesir- able activation of pyrite in sphalerite flotation is, therefore, a possible cause for concern Ferrous ions have been shown to activate sphalerite under certain conditions (Leroux et al, 1987; Zhang et al., 1992). However, the mechanism proposed was not necessarily limited to sphalerite, Possible activation of pyrite by ferrous ions is therefore a possibility. Finally, calcium ions, because they are usually present in large quantities (Cither from use of recycle water, presence of caleium-containing minerals and /or use of lime for pH adjustment) and are considered as depressants for pyrite (Fuerstenau et al, 1985), were also selected for study. ‘The classical approach to a fundamental study of metal ion effects would be to use single minerals. It is, however, becoming increasingly evident that this can be mislead- ing (Trahar et al., 1994; Nagaraj and Brinen, 1995). An example in our laboratories has been the different response of pyrrhotite and pentlandite to xanthate adsorption when in the presence of each other (Xu and Finch, 1996). Consequently, this study of the effect of metal fons on pyrite/xanthate interaction included the presence of sphalerite. ‘The interaction was followed by microflotation, infrared surface analysis, and zeta-potential ‘measurement, The implications for flotation practice are considered. 2. Experimental section 2.1, Minerals ‘The sphalerite (Sp) and pyrite (Py) samples (37-74 jum size fraction) were isolated from ore samples from Brunswick Mining and Smelting (New Brunswick, Canada) by alternate use of a shaking table and a Mozley separator. The single minerals obtained ‘were treated three times with a 5% HCI solution to remove soluble impurities. Residual sulphur, formed as a result of the acid treatment, was removed by washing the samples with acetone, followed by de-oxygenated-disilled water. The product was then dried in vacuum oven at ~ 70°C and stored under nitrogen. For both sphalerite and pyrite, X-ray diffraction analysis showed that no significant amounts of other mineralogical phases were present. Chemical analysis indicated a purity over 97% for pyrite while sphalerite contained 63.8% Zn and 2.8% Fe. The sample of this size range was used in the flotation and IR studies. For zeta-potential measurements, it was further ground (in fan agate mortar and pestle) to ca. 20 jum immediately prior to use. 2.2. Chemicals Sodium iso-propyl xanthate ['PrX, (CH,);CHOCS,Na] from American Cyanamid ‘was further purified using standard procedures and stored in petroleum ether (Rao, 1971a,b). ACS reagent grade copper sulphate, zinc sulphate, ferrous sulphate and calcium chloride (Fisher Scientific) were used as received. Hydrochloric acid andZhang era / mt J. Miner Process. 82(1997) 187-201 89 sizer 1 sine? Fig. 1. Set-up for conditioning of pyrite aloe (nineral 1) and in presence of sper (mineral 2) sodium hydroxide used as pH modifiers were also of ACS reagent grade. De-oxygenated double distilled water was used in all the experiments. 2.3, Mieroflotation ‘The set-up for conditioning the pyrite (Fig. 1) permitted the mineral to be treated alone (as mineral 1) or in the presence of sphalerite (as mineral 2), where the two ‘minerals were in separate compartment but shared the same solution. One gram of ‘mineral was conditioned for 10 min in 30 ml of de-oxygenated water at a given metal ion concentration, after which the supernatant was replaced with a premeasured amount ‘of xanthate stock solution, and conditioning continued for another 10 min. Conditioning ‘was provided by a laboratory shaker (New Brunswick Scientific Co., Inc., USA) at 200 rpm. To ensure that the minerals in the separate compartments shared the same solution in the case of the mixed-mineral tests, the level of the solution in the beaker was maintained above the top of the glass partition, as indicated in Fig. 1. The pyrite along ‘with the supernatant was then transferred to a modified Hallimond tube (Fuerstenau ct al, 1957), and flotation was conducted for 2 min with an air flow rate of 74 ml/min. ‘The solids in floats and tals were weighed separately aftr filtration and drying, and the recovery was calculated 24, Zeta-potential Zeta-potential of pyrite was measured using a Lazer Zee™ Meter (Model S01: Pen Kem, Inc., USA). All measurements were conducted in a 0.1 M NaCl background electrolyte solution. A 0.05 g sample of pyrite, alone or mixed with sphalerite (which was of much greater size). was placed in a 100 ml beaker and mixed, for 5 min, with 80 ml distilled water containing the metal ions of interest. (In some of the experiments. a pre-determined amount of xanthate was added at this stage and mixing continued for another 5 min.) The coarse sphalerite particles were then allowed to settle and supematant containing the fine target mineral particles was taken for zeta-potential measurement. The results presented in this paper are the average of three independent measurements with a typical variation of +2 mV. Repeat tests showed that the conditioning procedure was capable of producing reproducible mineral surfaces suitable for studying the effect of various treatments.190 Zhang era. / ne 1 Miner Process. 52 1997) 187-201 2.5. FTIR-spectrum The attenuated total reflectance (ATR) spectroscopic technique was used to character- ize the surface species on the mineral particles treated. (Sample preparation was the same as used for the microffotation tests.) A sample of the mineral along with some solution was taken using & pipette and placed on a strip of filter paper. This was repeated Aill the filter paper was covered by a thin layer of particles. The sample was then lifted along with the filter paper and pressed onto a zine selenide (ZnSe) ATR crystal. IR spectra were obtained using an IFS-66 FTIR spectrometer (Bruker) with a baseline horizontal ATR sampling unit (Spectra Tech). The clean ATR crystal was used ay background for the spectra presented in this communication. The spectrum was obtained by accumulating 200 scans using an MCT detector at a wavenumber resolution of 4 em. and presented without any baseline correction. As a check, a spectrum from the ZnSe crystal in contact with 10 * M_xanthate solution was acquired: no characteristic bands were observed in the spectral region presented in this communication, The crystal was cleaned with acetone, exposed to ultraviolet radiations for 10 min (to decompose any residual xanthate species), rinsed with 100% ethanol, and blow-dried with filtered dry nitrogen after each measurement For the purpose of IR band identification, the spectrum was also collected using external reflectance infrared spectroscopy (at a fixed incident angle of 45°) using a copper foil pre-treated in a 0.5 mM 'PrX solution. rinsed with petroleum ether and dried with dry nitrogen. This treatment removes. all dixanthogen components and leaves, to x 2 8 3 2 Fig 2. The effect of 10° M Cu ions om pyrite Notation with 10°" iso-popyl xa a 2 function ofp POX = pytite alone; PyCuX = copper scivted: Paspx =n the presence of spun: PrSpCaa = coppet- tivated in the presence of sphaleite,O Ahan etal / It J Miner. Proce. $2 (1997) 187-201 191 1 PK Pex Pyrex os 68 7 @ pH Fig, 3. The effet of 10°* M ferrous ions on pyrite Notation with 10°* M isopropyl xantate as fancton of pI PyX= pyrite alone; PyFeX = ion-activated: PySpFeX = iron-activated in the presence of sphaleit 10 _ Poe Prcak rseoax Recovery (%) se 7 o pH 4, The effec of 10°* Mf Ca ions on pyrite flotation with 10°* Mf iso-propy xamhate as function of pH YK = pytite alone: PyCaX = ealiumactvated; PySpCaX = cleiomactivated inthe presence of sphaerit.mm (2. Zhang ea / ne. Miner Process. 52 1987) 187-201 copper xanthate on the foil. The spectrum was collected using the same instrumental parameters as in ATR experiments, and polished copper foil was used as background, ‘The experiments for the mixed-mineral system were designed to eliminate galvanic effects which otherwise would complicate the analysis. This system is therefore different from that encountered in practice, but nevertheless it is a step closer compared to the traditional single mineral studies. Our focus in this work is to examine the effect of ‘metal ions and a second mineral on xanthate interaction with a target mineral (pyrite). The effect of galvanic interaction and redox potential was not examined, but for the purpose of comparison, we kept the redox potential relatively constant by using de-onygenated water with a low solid-to-tiguid ratio, In the case of mixed-mineral systems, quantifying the adsorption of metal ions or xanthate on individual minerals is difficult even if semi-quantitative XPS analyses were used. For this reason, we used zela-potential measurement as an analytical tool to provide in sity semi-quantitative information, which proved satisfactory 3. Results 3.1. Flotation Fig. 2 shows that pyrite alone (i.e. in the absence of metal ions and sphalerite) exhibited the well known flotation response: a minimum around pH 7, with increasing a . = & z : 4 3 Bs oy pH Fig, 5. Zot potenti of pyrite asa function of pH: alone (Px): i he presence of 10-* M Cu tons (PCuh 10° AF isorpropytxanthate (Py) bth Cv ions and xanhate (PyCu)0. Zhang oa / It J Miner. Process. 52 (1997) 187-201 13 floatability in acid conditions and a maximum in alkaline (ca. pH 8) (Steininger, 1968; Fuerstenau et al., 1985). The addition of cupric ions enhanced pyrite floatability significantly over the pH range 6 to 10. In contrast, in the presence of sphalerite along with metal ions, the floatability of pyrite decreased significantly over the whole pH range, with the recovery at pH > 5 being lower than that for pyrite alone without copper activation. This reduced floatability suggests competition for xanthate when the two ‘minerals share the same solution. It appears that when copper-activated sphalerite is present, it consumes most of the xanthate available, leaving a lower xanthate concentra- tion for pyrite flotation than if the sphalerite were not present. This was indirectly confirmed by the observation that the flotation of pyrite in the presence of sphalerite but absence of cupric ions remained unchanged, because in the absence of activating metal ions, sphalerite is largely unresponsive to xanthate. This suggests that the presence of sphalerite under these conditions should have litle effect on pyrite flotation, as observed. Fig. 3 shows the effect of ferrous ions on pyrite flotation. Similar to cupric ions, ferrous ions increased floatability of pyrite alone, in particular in alkaline media with ‘maximum recovery at ca. pH 9. Again, in the presence of sphalerite, pyrite flotation was depressed. An activation effect of calcium ions (10"* M) on single pyrite flotation was found although it was less than that of either cupric or ferrous ions (Fig. 4). When sphalerite is present, however, pyrite is virtually unfloatable above pH 7. x ° S & z « a 3 = 3 3 R «© = * s Fig. 6, Zatapotertal of pyrite aa fonction of pH inthe presence and absence of spheric: sone (Py) inthe presence of 10°? M Cu toms (P3Cul with added sphalente (PyCuSp); in 10° M isosropyl xantate (scars).194 Zhang eral. /Ine. 1. Miner Process. 521997) 187-201 ‘The above flotation results all show a common feature: metal ions promoted flotation Of pyrite alone, but the presence of sphalerite along with the metal ions depressed the foatability 3.2. Zeta-potential Fig. 5 shows that pyrite alone had an iso-electrical point (iep) at ca. pH 3. This value is lower than that reported by Fuerstenau and Mishra (1980), but similar to that by Fomasiero et al. (1992). The discrepancy appears to be related to the initial oxidation state of pyrite: the more oxidized the pyrite, the higher the iep. By comparison with the iep of pyrite oxidized to various degrees as reported by Fomasiero et al. (1992), the pyrite sample used in this study appears to be slightly oxidized In the presence of 'PrX, the zeta-potential of pyrite decreased marginally (by inspection of the data points), probably reflecting adsorption of negatively charged xanthate anions. A similar observation was made by Fomasiero and Ralston (1992) although Cases et al. (1993) suggest a much larger decrease in zeta-potential in the presence of xanthate, Cupric ions increased the zeta-potemtial significantly. in particular above pH 6. This increase can be attributed to the adsorption of a cupric ion species (probably Cu(OH)* from reference to the solution stability diagram (Stumm and Morgan, 1996) on the negatively charged pyrite surface. Upon subsequent addition of épotential (mV) & pH Fig, 7, Zeta potetial of pyrite a a fnetion of pH inthe presence and absence of ferous ions and sp alone (Py): in the presence of 10°" Af ferous ions (P4Fe); with added sphalerite(PvFeSp): and in 10 ‘so-popyl anthate(PyFeXSp),Q. Phang etal, It J Miner. Process, 52 (1997) 187-201 195 xxanthate at alkaline pH, the zeta-potential decreased significantly. The reduction can be attributed to either the adsorption of negatively charged 'PrX ions and/or to partial removal of adsorbed cupric ions from the pyrite surface. The increased flotation recovery of pyrite with 'PrX in the presence of cupric ions suggests that the former is more likely to be the case, ic. the presence of cupric ions on the surface attracts the negatively charged 'PrX. Fig. 6 shows the effect of the presence of sphalerite. The zeta-potential in the presence of cupric ions remained the same whether sphalerite was present or not. The subsequent addition of 'PrX did not change the zeta-potential, which is in marked contrast to the case in the absence of sphalerite. By comparison with Fig. 5, copper ions appear to be still adsorbed on pyrite in the presence of sphalerite, but subsequent xanthate adsorption did not occur. This finding is consistent with the observed flotation behaviour, namely that a significant reduction in pyrite flotation occurred when spha- lerite was present (Fig. 2). Shown in Figs. 7 and 8 are the zeta-potential results in the presence of ferrous ions ‘and calcium ions, respectively. Similar to the case with cupric ions, these ions increased the zeta-potential of pyrite significantly. In the presence of sphalerite, however, the 2eta-potential response resembled that of pyrite alone and the subsequent addition of *PrX had little effect. This suggests that ferrous and calcium ions have much less affinity for pyrite compared to sphalerite and adsorbed preferentially on sphalerite when these 2 S04 S CG 2 oa = 2 5 «© 0 : «6 & ww pH Fig. &, Zeta-potemial of pyrite asa function of pH in the presence and absence of calcium ions and sphaerite: sone (Py) in the presence of 10°? Mf caleum ions (PYCa}: with added sphalerie (PyCaSp?; in 10-* Mt Jso-propy xanthan (PyCaXSp),196 (0. Zhang era / tt J. Miner Process 52 (1997) 187-201, jo IR Unit 4350 1300 1250 1200 1180 1100 1050 1000 950 ‘Wavenumber [em] Fig, 9, FTIR/ATR spectra of pyrite panicles ueated with 10° M cupric ons and 3% 10° M iso-peopsh ante in the absence (c) and presence (A) of spalerte, a compared to that untested (a) o treated with Aamtateoaly(b), and to extemal reflectance spectrum of copper fil eae with io-propyl xanthate ‘wo minerals are present in the same solutions. The competition mechanism for the observed suppression of metal activation in the presence of sphalerite seems to depend 6 the metal ion: in the ease of cupric ions, xanthate adsorption was suppressed while in the case of ferrous and calcium ions, adsorption of the metal ions was suppressed. The overall effect, however, is similar, namely, the presence of sphalerite retarded the flotation of pyrite. 3.3. Infrared spectra Infrared spectroscopy was used to identify and quantify the surface species resulting from interactions between the minerals and 'PrX. Fig, 9 shows the spectra obtained with pyrite in the presence of cupric ions. (Only part of the spectral region, from 1350 10 950 em-', is shown, over which the characteristic xamthate bands appear.) A featureless spectrum was obtained for the pyrite conditioned in de-oxygenated water (a). Six broad bands at ca. 1267, 1256, 1142, 1088, 1026 and 1008 cm were observed when pyrite was conditioned in 5X 10-* M 'PrX solutions (b), suggesting the adsomption of 'PrX on2. Zhang eal / nt. Miner Process. 52 (197) 187-201 7 “Table t Positions of coresponding principal bands (cm) of copper nanthate and dxanthogen formed from ethyl and iso-propyl xamhates Compound ‘Vibration moder 4 (SCS, COC) vicoo oo) &, 161 1240 7130 Tos 088 Tos (a0, 1261 1286 a2 88 1026 1008 cuEX ust 1190 123 1039 13s 1009 cuPx 1239 im a0 1050 1016 1008 pyrite. Comparing these bands with those (1239, 1227, 1216, 1090 and 1016 em” ') on copper foil (e) it is evident that the adsorbed species is dixanthogen, as expected in the ‘case of pyrite (Ball and Rickard, 1976; Woods, 1984). The dixanthogen bands corre- sponded to those of ethyl dixanthogen (Leppinen et al., 1989; Yoon et al., 1995), but with a slight shift as shown in Table 1. These spectral shifts are associated with substitution of the ethyl group by iso-propyl which is a stronger electron donor. When IR Unit 1350 13001250 1200 1150 1100 1050 1000950 ‘Wavenumber {em} Fig, 10. FTIR/ATR spectra of paricles trated with cupric (), ferrous (8) and alcium (e) tons in the presence of 5%10"* M is0-propyl xanthate as compared to that untreated (a) and weated with xanhute only ©.