Sinter Formation in Zinc Roasting

Sinter formation in zinc roasting
, J. Richards, A. Walliser and D. Bessinger T. Coetsee*, G. Naude

Published by Maney Publishing (c) IOM Communications Ltd and the Australasian Institute of Mining and Metallurgy
Excessive sinter formation in zinc roasters leads to defluidisation of the bed so that production time is lost in clearing the collapsed bed from the roaster in preparation for restart of the roaster process. At Exxaros Zincor plant the roaster feed concentrate consisted of a blend of Rosh Pinah, Black mountain and an import concentrate. The possible formation of unwanted sinter material was investigated by thermochemical simulation of the roaster process using FactSage software. The mineralogical composition of the individual feed concentrate streams was quantified by QemScan analyses. This mineralogical analysis was simplified and then used as input into the FactSage simulation calculations. The thermochemical simulation results were used to aid in the process interpretation of mineralogical analyses of samples from a failed bed, as compared to an acceptable roaster product sample.
Keywords: Zinc roasters, Sinters, Impurities, Phases
Introduction
Zincor was the primary zinc producer in South Africa, situated in Springs. The plant was mothballed in 2011. The plant operated four Lurgi uidised bed roasters in which zinc sulphide concentrate was roasted: two small roasters each rated at 5 t h21 dry feed and two larger roasters each rated at 11 t h21. From time to time sinter formation in the roasters occurred. This work forms part of the effort to obtain a better understanding of the reasons for sinter formation in the roasters. The work consists of characterisation of the feed concentrate streams, thermodynamic modelling of the roasting process and comparison of sintered samples from the roaster to acceptable roaster product.
Previous studies
In the roasting of zinc sulphide concentrates the unwanted formation of sintered material is prevented through close control of concentrate chemistry and process operational parameters, e.g. sufcient oxygen feed and distribution, temperature control in the roaster bed and freeboard, impurity level control in the feed concentrate blend (Nyberg, 2004). The general rule used to prevent sinter formation is based on limiting impurities in the concentrate feed to the roaster to PbzCuzSiO2,5%, but is not well founded (Grant, 1994). Molten phases can be present in the form of sulphide melts formed from impurity elements Pb, Cu, Fe, Zn, sulphate melts formed from impurity elements Na, K, Pb and oxide melts formed from impurity elements Pb, Cu, Si and Zn (Nyberg, 2004). Several studies have been carried out on sinter formation in zinc sulphide roasting. The complex interaction between concentrate chemistry and roaster operational parameters in terms of general chemistry
Exxaro Resources, PO Box 9229, Pretoria 0001 South Africa *Corresponding author, email theresa.coetsee@exxaro.com
was explained in detail before (Hodder, 2005). Because each sulphide concentrate is somewhat different from the next, the particular feed concentrate chemistry and mineralogy should be considered in setting roaster operational parameters. Synthetically prepared FeS, (Zn,Fe)S and pure ZnS were reacted in an experimental setup to investigate agglomeration of these sulphides (Benlyamani and Ajersch, 1986). Only solid state sintering was observed in ZnS reacted at 1050uC. When FeS was reacted at 950uC a liquid phase was seen to wet entire grains and ll pores. At 1050uC increased liquid phase formation was seen to such an extent that the liquid phase was ejected from the crucible. The synthetic (Zn,Fe)S agglomerated to an extent intermediate between that of FeS and ZnS at 1050uC. The intergranular liquid phase responsible for agglomeration consisted of FeSO containing 60 65%Fe, and possibly containing some Zn. The large grains consisted of ZnO and ZnFe2O4. An industrial concentrate was reacted under the same conditions as the synthetically prepared (Zn,Fe)S at 1000uC resulting in similar sintering morphology and reaction products to that when (Zn,Fe)S was reacted. From this work the conclusion is that liquid phase formation at elevated roasting temperatures is possible, even when Pb, Cu and Si impurities are absent. Sinter formation in zinc concentrate reacted at 1100uC, in laboratory experiments to simulate roasting, is caused by formation of a liquid phase of ZnSO composition (Shu et al., 1999). Agglomerate collected from a deuidised industrial roaster was mineralogically analysed (Chen and Dutrizac, 2004). The binder phases were identied as zinc oxysulphate, Zn3O(SO4)2 and hydrated zinc sulphate, ZnSO4.nH2O. The binder phases cemented normal agglomerated particles and normal calcine particles into a lump. Trace quantities of Zn2SiO4 and PbSO4 were identied in the X-ray powder diffraction analysis. The authors ascribed the formation of this agglomerate to
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improper roasting temperature and/or moisture content, but maintains that Pb, Cu and SiO2 impurity content is important.
Experimental
Feed and product samples
The concentrate mixture to the roasters consisted of a mixture of Black Mountain, Rosh Pinah and an imported concentrate. Each feed concentrate was analysed by Qemscan. In normal roaster operation some agglomeration of the feed concentrate particles of 245 mm is normal. At Zincor the roaster bed overow is sampled each day and the percentage of particles larger than 1 mm is measured. An acceptable portion of z1 mm particles is 2025%, while more than 50% z1 mm is a sign of bed failure development and is not acceptable. Three samples were collected for mineralogical analyses. The sample details are as follows: (i) an acceptable roaster product sample taken from the bed overflow (ii) a sinter sample taken from the nozzle grate area after fluidised bed shutdown (iii) a bed overflow sample taken in the period of fluidised bed collapse developing
analytical conditions include an acceleration voltage of 25 kV, 275 000 counts/s pulse processor and gold and quartz standards were used to calibrate the backscatter electron intensities. Measurements were performed at a 2 mm point spacing grid. High resolution backscatter electron images were collected with an acceleration voltage if 25 kV.
Results and discussion

Feed concentrate characterisation
An extensive list of minerals was generated from the Qemscan analysis. This mineralogical analysis was simplied to that shown in Table 1 so that the mineral composition in Table 1 corresponds to minerals contained within the FactSage database. The simplied mineral composition was calculated to yield the same elemental analysis as that from the extensive mineral analysis. The concentrate mixture is composed of 29% Black Mountain, 26% Import and 45% Rosh Pinah.
Thermodynamic process modelling

FactSage simulations were carried out to determine the thermodynamically stable phases across the range of plant roasting conditions. The simulation conditions are summarised in Table 2. The oxygen ratio is dened as the moles of oxygen in the process gas feed divided by the moles of oxygen required to react the feed mixture to stable oxides and sulphates. The mineral phases in the concentrate react with oxygen according to the stoichiometry of reactions (1)(6) 3 ZnSz O2 ?ZnOzSO2 2 CuFeS2 z 2FeS2 z 11 1 O2 ?CuOz Fe2 O3 z4SO2 2 2 (1)
Thermodynamic modelling
The possible formation of unwanted sinter material was investigated by thermochemical simulation of the roaster process using FactSage software. The thermochemical simulation results were used to aid in the process interpretation of mineralogical analyses of samples from a failed bed, as compared to an acceptable roaster product sample.
Mineralogy
Bulk chemistry of the feed concentrates and the three product samples was determined by inductively coupled plasma. The crystalline composition of the product samples was determined by X-ray diffraction (XRD) and phase composition by scanning electron microscopy (SEM) analyses. Care was taken not to dissolve water soluble phases from the product samples by using parafn as polishing liquid to prepare polished sections. Analyses by XRD were carried out using a Panalytical XPert Pro diffractometer with XPert HighScore Plus software and Co Ka radiation. The data collected were compared with reference data in the ICDD (International Centre for Diffraction Data) database and best t identications were determined. Semiquantitative sample compositions were determined using the reference intensity ratio method. Qemscan investigation of the feed concentrates was carried out using a Qemscan E430, Zeiss EVO50 SEM platform, tted with Bruker AXS Xash X275HR detectors. The analytical conditions used for SEM/EDS analyses included an acceleration voltage of 15 kV, beam current of 11 mA, specimen current of 5 nA, 90 000 counts/ s pulse processor and a working distance of 22?5 mm. The quantication software and hardware were calibrated using the copper standard. The quantication Bruker Quantax Esprit v1?8?2 software was used and entails a standardless quantication method incorporating the PbZAF correction. The Exxaro PbZn-Sip (species identication protocol) key le was used for the Qemscan analyses. The Qemscan
(2)
11 O2 ?Fe2 O3 z4SO2 2
(3)
CaMgCO3 2 z2SO2 zO2 ?CaSO4 zMgSO4 z2CO2 (4) PbSz2O2 ?PbSO4 (5)
Table 1 Mineralogical concentrates Phase ZnS CuFeS2 FeS2 SiO2 BaSO4 CaMg(CO3)2 PbS FeS MnSiO3 KAlSi3O8 Fe3O4 Al2O3 Total PbzCuzSiO2 Mixture 82.1 0.7 2.5 0.7 0.4 2.4 3.4 5.1 1.4 0.5 0.7 0.2 100 5
input Black Mountain 79.6 0.5 1.1 0.5 0.1 0.1 2.0 14.1 0.9 0.1 0.8 0.2 100 3
composition
of
feed
Import 91.3 0.9 1.1 0.4 0.1 1.9 0.3 1.6 1.4 0.1 1.0 0.0 100 1
Rosh Pinah 78.5 0.8 4.2 1.0 0.7 4.1 6.1 1.2 1.7 1.0 0.4 0.3 100 7
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1 Solids phases at oxygen ratio of 0?84
7 2FeSz O2 ?Fe2 O3 z2SO2 (6) 2 Zincite, spinel and willemite are present under all simulated conditions. Similar minor solids phases are formed under reducing conditions (oxygen ratios of 0?84 and 1?00) (see Fig. 1 and 2). Only the proportions of solids phases differ with more unreacted sphalerite at oxygen ratio of 0?84 with the resultant smaller quantity of zincite formed. Under oxidising conditions (oxygen ratio of 1?19) markedly different phases are formed compared to those formed under reducing conditions (see Fig. 3). In addition, a smaller number of phases are formed. Sulphates are stabilised at all temperatures under oxidising conditions, and more so at lower temperature. At 800uC the main phase is ZnSO4 at 55 mass-%, and only 23 mass-% zincite is formed. The other sulphates formed are Ca(SO4) Mg(SO4), PbSO4, MnSO4 and K2Ca2(SO4)3, compared to only BaSO4 and K2SO4 formed under reducing conditions. Under oxidising conditions only one silicate is formed, willemite. Under reducing conditions several silicates are formed: willemite: (Zn,Mg)2SiO4, olivine: (Mg,Fe,Ca,Mn)2SiO4, mellilite: (Ca,Pb)2[Zn,Fe2z,Fe3z, Al](Fe3z,Al,Si)2O7. According to the FactSage simulation outputs none of these silicates are molten at 8001000uC.
Table 2 Simulation conditions for FactSage Oxygen ratio* kg O2/t dry mixture feed kg N2/t dry mixture feed Nm3 O2/t dry mixture feed Nm3 Air/t dry mixture feed kg H2O/t dry mixture feed 0.84 400 1400 0 1400 100 1.00 451 1400 36 1400 100 1.19 563 1400 114 1400 100
Under reducing conditions lead is present in the matte phase as well as PbS at 800uC. In comparison, lead is present only in the matte phase at 900 and 1000uC. Under reducing conditions increasing quantities of lead in the form of PbS, up to 26 kg Pb/t dry concentrate feed, reports to the gas phase with increasing temperatures as shown in Fig. 4. Concurrently, the lead content of the matte phase is reduced as shown in Table 3. Only a small quantity of lead is volatilised to the gas phase at 1000uC under oxidising conditions. This lead is present as PbO. The simulation results show that among the metallic compounds present in the concentrate feed only lead is volatilised to quantities higher than 1 kg h21 for 1 t dry concentrate feed at 8001000uC. Copper is present in the matte phase under reducing conditions. Under oxidising conditions copper is present as CuO at 800 and 900uC and as Cu2O at 1000uC. The results show the importance of sufcient oxygen feed to the roaster to attain maximum sulphur conversion and prevent matte formation. Variation of the reaction temperature results in little phase variation as compared to the effect of oxygen feed quantity variation on the types of phases formed. The only liquid phase present in the simulation results is the matte phase formed under reducing conditions. Only up to 12 kg matte/t dry concentrate feed can be formed. This quantity seems to be too small to be solely responsible for a bed failure.
Product samples
From the similar bulk chemistry analyses of the three sinter samples, as shown in Table 4, it is clear that chemistry alone cannot provide sufcient information to determine the difference between these samples, mineralogy is required as well. The XRD analyses of the three product samples are shown in Table 5 below. Sample 1 contains some uncalcined sphalerite, but consists mostly of zincite and zinc
*Oxygen ratio5kg mol O2 in air and oxygen gas feed/kg mol O2 required for complete oxidation of concentrate feed mixture.
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ferrite. This is the typical mineralogical constitution of normal zinc roaster product. Some of the zincite phases in samples 1 and 3 still contain iron, indicating that nal stage roasting did not take place in all the particles. Samples 2 and 3 were taken after and during roaster bed failure. Sample 3 is partially calcined concentrate as indicated by the large proportion of uncalcined sphalerite present. In
contrast, sample 2 contains basic zinc sulphate (BZS) as the main phase. Zinc sulphate (ZnSO4.H2O) and zincite (ZnO) are present as major phases. Basic zinc sulphate is stable at 760825uC, and ZnSO4 is stable ,760uC (Hodder, 2005). The hydrated zinc sulphate ZnSO4.H2O decomposes to anhydrous zinc sulphate when heated above 238uC. According to the
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4 Mass-% distribution of Pb to gas phase
FactSage stability diagrams, BZS is formed below 500uC. This indicates that the temperature conditions where this accretion formed was below the accepted
Table 3 Composition of matte phase Oxygen ratio Temperature/uC Pb Zn Cu S Total 0.84 800 62 2 20 16 100 0.84 900 53 5 25 17 100 0.84 1000 30 10 39 20 100 1.00 800 62 2 20 16 100 1.00 900 53 5 25 17 100 1.00 1000 30 10 40 20 100
5 Image (SEM) of BZS and zinc sulphate binder phase appearance in sample 2
normal operating temperature for roasters at 850 950uC. Basic zinc sulphate and zinc sulphate were identied in previous work to be the binder phases that enabled agglomeration of normally roasted particles (Chen and Dutrizac, 2004). These binder phases appear as a uffy crust in the SEM image. The SEM image for sample 2 shown in Fig. 5 is quite similar in appearance to the reported binder phases.
Table 4 Bulk chemistry of three sinter samples Sample 1: acceptable bed overflow sample SiO2 Al2O3 Fe2O3 CaO MgO Mn K2O Zn Cu Pb Ba S Total *LOI 2.5 0.5 10.5 1.5 0.7 1.0 0.1 61.6 0.8 2.6 0.2 1.9 83.8 2.02 Sample 2: nozzle grate area crust 1.3 0.3 5.1 1.3 0.6 0.7 0.1 45.7 0.5 1.8 0.2 11.3 68.7 30.3 Sample 3: bed overflow sample 2.0 0.5 11.1 1.6 0.8 1.1 0.1 59.8 0.8 0.0 0.3 10.1 88.2 7.23
*LOI: loss on ignition. Table 5 Semiquantitative XRD analyses of sinter samples/mass-% Mineral Zincite Gunningite Zinc oxide sulphate Franklinite Willemite Wurtzite Sphalerite Anglesite Magnetite Hematite Rutile Quartz Cristobalite Clinopyroxene Approximate formula ZnO ZnSO4.H2O Zn3O(SO4)2 (Zn0?54Fe0?46)Fe2O4 Zn2SiO4 ZnS ZnS Pb(SO4) Fe3O4 Fe2O3 TiO2 SiO2 SiO2 MgSiO3 Sample 1: acceptable bed overflow sample 70 Sample 2: nozzle grate area crust 13 27 38 6 4 Sample 3: bed overflow sample 41
20 4 3
3 3 39 14
2 2 6 2 1 1 2
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6 Image (SEM) of sample 3
7 Image (SEM) of liquid phase coating of zincite crystals in sample 3
The reason for incomplete calcination can be varied, e.g. insufcient oxygen feed in the blast, uneven distribution of blast in the roaster, temperature variation and/or reaction mechanisms, e.g. barriers form around reactant particles and prevent oxygen from reacting with the sphalerite particle. The particle morphology in sample 3 is variable as some particles are completely roasted, while others did not roast at all. The unroasted zinc sulphide phase areas appear somewhat rounded, but were not molten. There is no particular phase seen to be responsible for agglomeration or closing off of the zinc sulphide particles from reactant oxygen gas. The only clear indication as to the reason for incomplete roasting in sample 3 is the three-dimensional images in Figs. 6 and 7. This phenomenon of hexagonal zincite crystals covered by a molten phase has been identied before (Shu et al., 1999). The zinc concentrate was partially roasted in a laboratory experiment at 1100uC for 5 min. Although PbO formation at the surface of the sintered samples was observed, it was concluded that the quantity of Pb in the zinc concentrate was too low to be the main cause of sintering. The authors concluded that the liquid phase coating was not due to a specic contaminant, but probably due to a low melting point phase area in the ZnSO system, similar to that in the FeSO system. Analyses of the apparent molten phase in Fig. 7 are shown in Table 6. No signicant liquid phases were identied from FactSage calculations for the analyses in Table 6 at 8001200uC. However, the analyses at least show that lead is not present in the molten phase and the molten phase compositions are in agreement with previous work (Shu et al., 1999). In fact, no Pb was analysed in sample 3, indicating that most of the Pb was volatilised. The plate-like shape of the hexagonal zincite crystals, instead of round shaped crystals, have been linked to high temperature phase composition of zincite above
Table 6 Analyses of molten phase in Fig. 7 Fe 7 4 7 16 O 11 3 28 21 Zn 58 64 45 46 Mn 3 1 3 2 Cu 1 0 0 0 S 20 28 16 14 Total 100 100 100 100
1200uC when the solubility of Fe in zincite increases rapidly (Hansson et al., 2004). Another indicator of overheating in sample 3 is the presence of wurtzite in the XRD result in Table 5. Wurtzite is stable above 1019uC. In terms of the presence of silicates in the sinter samples, the silicates formed in samples 1 and 2 are of willemite stoichiometry and contain different quantities of Fe, Mn, Mg, Ca that, in most instances, lower the liquidus temperature from 1513uC. Only two phase areas of CaAlsilicate were analysed in sample 3. None of these silicate phases were fully liquid at the typical roaster operating temperatures of 850950uC. From the mineralogical analyses of samples 2 and 3 above, it can be concluded that divergent oxygen potential conditions were present within the roaster due to variable operating conditions in terms of oxygen feed and/or distribution. This in turn resulted in divergent temperature conditions in the reactor outside the operational set point band. The exact reason for this is most likely uneven distribution of blast through the bed so that low temperature oxidising conditions prevailed close to the blast nozzle grate area to form sample 2 type material, and high temperature reducing conditions prevailed in the bed to form sample 3 type material.
Conclusion
The FactSage simulation results show that the phase constitution of reacted sphalerite roaster concentrate varies primarily with oxygen addition to the process, while the effect of temperature on phase constitution is limited at 8001000uC. The mineralogy of the sintered samples in this work shows that sinter formation was caused by divergent oxygen potentials within the roaster due to variable operating conditions in terms of oxygen feed and/or distribution. This condition caused variable temperatures inside the reactor outside the operational set point band so that low temperature oxidising conditions prevailed close to the blast nozzle grate area to form sample 2 type material, and high temperature reducing conditions prevailed in the bed to form sample 3 type material. In this work, the rule that is generally used to prevent sinter formation in zinc roasters: limiting impurities in the concentrate feed to the roaster to PbzCuzSiO2,5%,
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could not be linked to any phases formed that caused sinter formation.
References
Benlyamani, M. and Ajersch, F. 1986. Agglomeration of particles during roasting of zinc sulfide concentrates, Metall. Trans., 17B, 647656. Chen, T. T. and Dutrizac, J. E. 2004. Mineralogical changes occurring during the fluid-bed roasting of zinc sulfide concentrates, JOM, 56, (12), 4650. Grant, R. M. 1994. Emerging developments in zinc extraction metallurgy, Proc. 2nd Int. Symp. on Metallurgical processes for the year 2000 and beyond and the 1994 TMS extraction and
process metallurgy meeting, (ed. H. Y. Sohn), 125149, San Diego, CA, TMS. Hansson, R., Hayes, P. C. and Jak, E. 2004. Phase equilibria in the ZnO-rich area of the FeZnO system in air, Scand. J. Metall., 33, (5), 294304. Hodder, D. G. 2005. The mechanism of accretion formation during the fluid-bed roasting of zinc concentrates, Proc. Int. Symp. on Lead and Zinc Processing, (ed. T. Fujisawa), 279301, Kyoto, Japan, The Mining and Materials Processing Institute of Japan. Nyberg, J. 2004. Characterisation and control of the zinc roasting process, PhD thesis, University of Oulu, Oulu, Finland. Shu, J., Lakshmanan, V. I. and Convey, J. 1999. Sintering and ferrite formation during high temperature roasting of sulfide concentrates, Can. Metal. Q., 38, (4), 215225.
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Sinter formation in zinc roasting

, J. Richards, A. Walliser and D. Bessinger T. Coetsee*, G. Naude

Mineral Processing and Extractive Metallurgy (Trans. Inst. Min. Metall. C)