A NOVEL METHOD FOR METAL RECOVERY FROM ZINC & LEAD SLAGS

Transcription

1 A NVEL METHD FR METAL REVERY FRM ZINC & LEAD SLAGS by YANJUN ZHANG B. Eng., Nrtheastern University, P. R. China, 1995 A THESIS SUBMITED IN PARTIAL FULFILLMENT F THE REQUIREMENTS FR THE DEGREE F MASTER F APPLIED SCIENCE in THE FACULTY F GRADUATE STUDIES DEPARTMENT F METALS AND MATERIALS ENGINEERING We accept this thesis as cnfrming t the required standard THE UNIVERSITY F BRITISH LUMBIA June 2003 YANJUN ZHANG, 2003

2 In presenting this thesis in partial fulfilment f the requirements fr an advanced degree at the University f British Clumbia, I agree that the Library shall make it freely available fr reference and study. I further agree that permissin fr extensive cpying f this thesis fr schlarly purpses may be granted by the head f my department r by his r her representatives. It is understd that cpying r publicatin f this thesis fr financial gain shall nt be allwed withut my written permissin. Department The University f British Clumbia Vancuver, Canada Date DE-6 (2/88)

3 11 ABSTRACT Cnventinal zinc fuming frm lead blast furnace slags cannt cntinue when zinc and lead cntents are belw wt.% and wt.% respectively, because f slid irn frmatin, which als causes the frmatin f accretins, ming f slag, and cntaminatin f the fume. A new methd, electrreductin, was develped in a previus study t recver the heavy metals zinc, lead, indium and germanium frm final zinc fumer slag. A series f experiments was als cnducted in this study using tw types f fumer slag frm MIN. Zinc cntent was 4.5wt% in ne slag and 1.5wt% in anther slag. Experimental data indicated that abut 50% f the zinc and mst f the lead culd be remved frm bth slags by 90 minute f electrrefining. Fllwing the wrk n the fumer slags, a study was cnducted n the ptential t reduce lead and zinc directly frm MIN's Kivcet slag (cntaining abut 16 wt% zinc and 10 wt% lead) and ptentially bviate the need fr slag fuming. Metal recvery frm the Kivcet slag was examined using the three methds used fr the fumer slag study: hlding at temperature t allw the divalent irn t reduce the metal ins int the gas phase; equilibratin with a cpper "getter"; and electrreductin int a liquid cpper cathde using a graphite ande. The presence f metallic lead and carbn in the Kivcet slag has a significant influence n the recvery f metal frm the slag in subsequent prcessing. Hlding f the slag at temperature permitted the recvery f much f the metallic lead as vapr and sme small recvery f zinc as fume. When cpper was used as a getter, mre zinc and lead were recvered. In electrrefining, lead recvery was much higher than that in equilibrating with cpper, but there was n bvius enhancement in zinc recvery. A series f experiments were als cnducted in which the Kivcet slag was treated t remve sme f the zinc and the lead and then was electr-refined three times. Zinc and lead cntents in thefinalslag decreased t 5.9% and 0.3% respectively. Althugh mst f the lead was recvered, further refining wuld still be required t capture the remaining zinc metal.

4 Ill TABLE F NTENTS ABSTRACT TABLE F NTENTS LIST F FIGURES LIST F TABLES ACKNWLEDGMENTS ii iii iv vi vii 1. INTRDUCTIN 1 2. THE SLAGS FRM MIN 3 3. LITERATURE REVIEW THE KTVCET PRCESS THER PYRMETALLURGICAL LEAD AND ZINC PRCESSES PYRMETALLURGICAL PRCESSES FR ZINC-BEARING SLAGS AND RESIDUES PRPERTIES F ZINC-LEAD SLAGS Activities f Zn and Fe in Zinc-bearing Slags Cnductivity f Zinc-Lead Slags The Hall-Herult Prcess BJECTIVES FACT CALCULATIN N THE KIVCET SLAG EXPERIMENTAL EXPERIMENTAL APPARATUS METHDLGY Metal Recvery Electrical Resistance Measurement RESULTS AND DISCUSSIN METAL REVERY Metal Recvery frm the Fumer Slags Metal Recvery frm the Kivcet Slag ELECTRICAL RESISTANCE MEASUREMENT NUSINS 84 REFERENCES 87 APPENDIX-1: ANALYSIS F THE SLAG SAMPLES AND THE CRUCIBLE 91 APPENDIX-2: ANALYSIS F THE FUME SAMPLES 127 APPENDIX-3: ANALYSIS F THE PPER BUTTNS 134

5 iv LIST F FIGURES Fig. 1: Theflwsheet f the Cminc's integrated zinc-lead peratins 4 Fig. 2: SEM image f a Kivcet slag particle 7 Fig. 3: SEM image f a blight spt 8 Fig. 4: EDX analysis f ne bright spt 9 Fig. 5: EDX analysis f anther bright spt 10 Fig. 6: SEM image f a black spt 11 Fig. 7: verall analysis f the black spt (with EDX) 12 Fig. 8: EDX analysis f Area-1 in the black spt 13 Fig. 9: EDX analysis f Area-2 in the black spt 14 Fig. 10: EDX analysis f Area-3 in the black spt 15 Fig. 11: Schematic diagram f the experimental apparatus 31 Fig. 12: Inductin furnace 34 Fig. 13: Assembly f the crucible 36 Fig. 14: Schematic diagram f the fume cllectin device 37 Fig. 15: Schematic diagram f slag and cpper resistance measurement 42 Fig. 16: Schematic diagram f resistance measurement in electrrefining 43 Fig. 17: The change in Ca and Si02 cntents f fumer slags with time 45 Fig. 18: Increase in the weight f fumer slags with time 45 Fig. 19: Analysis f Zn and Pb in the high residual fumer slag, uncrrected 47 Fig.20: Zinc and lead lss by slag reheating-high residual 47 Fig.21: Zinc lss by slag reheating -Lw residual 49 Fig.22: Zinc and lead lss with cpper getter-high residual 51 Fig.23: Zinc and lead lss with cpper getter-lw residual 53

6 LIST F FIGURES (cnt.) Fig. 24: Typical Current-Vltage-Time recrd 55 Fig. 25: Cmparisn f zinc recveries - High residual electrreductin 55 Fig. 26: Cmparisn f lead recveries - High residual electrreductin 56 Fig. 27: Cmparisn f zinc recveries - Lw residual electrreductin 56 Fig. 28: Change f Si0 2 and Ca cntents in the Kivcet slag 60 Fig. 29: Increase f slag weight with time - Kivcet 61 Fig. 30: Metal recveries in the hlding runs withut cpper - Charge mix 64 Fig. 31: Decrease in in equivalents during different melting perid and 64 mles f electrns intrduced in electrrefining - Charge mix Fig. 32: Metal recveries in the hlding runs with cpper - Charge mix 66 Fig. 33: Typical ptential and current in electrrefining - Charge mix 69 Fig. 34: Cmparisn f metal recveries in electrrefining and 70 equilibrating with cpper - Charge mix Fig. 35: Reductin f Kivcet slag in the electrrefining runs in which 72 5 vlts was applied after 90 minutes Fig. 36: Metal recveries frm the slag during electrrefining 3 times 74 Fig. 37: Drp f in equivalents and electrns (mles) supplied 75 during electrrefining 3 times Fig.38: Ttal electrical resistance in slag measurement - High residual 77 fumer slag Fig.39: Ttal electrical resistance in slag measurement - Lw residual 78 fumer slag Fig.40: Ttal electrical resistance in slag measurement - Kivcet slag 78 Fig.41: Ttal electrical resistance in cpper measurement 81

7 VI LIST F TABLES Table 1: Analysis f the slags frm Cminc 5 Table 2: Analysis f typical LBF slag 19 Table 3: Analysis f typical ISP slag 19 Table 4: Specific cnductances f sme xides near their melting pints 22 Table 5: Results f FACT calculatin n the Kivcet slag 28 Table 6: Fume analysis - Fumer slag 48 Table 7: In equivalents in the fumer slags 50 Table 8: Cpper buttn analysis - Fumer slag 52 Table 9: Zinc cntent in high residual fumer slag befre and after 57 treatment (90 minutes) Table 10: Analysis f the fume - Kivcet 61 Table 11: Analysis f the charge-mixture and the final slags 62 Table 12: Analysis f the cpper buttns - Charge mix 67 Table 13: Zinc and lead balance in hlding with cpper and 68 electrrefining - Charge mix Table 14: Vltage distributin in electrrefining 83

8 Vll ACKNWLEDGMENTS I wuld like t express my gratitude and thanks t my research supervisr, Prfessr Ray Meadwcrft, fr prviding me the pprtunity t wrk with him in the Department f Metals and Materials Engineering at UBC. His advice, instructin and encuragement were very helpful and made the prject an enjyable learning experience. Assistance with sme f the experimental wrk prvided by Mr. Peter Musil, Research Technician, is really appreciated. Thanks are als due t many culty and staff in this department. I wuld als like t thank Dr. Greg Richards in Teck Cminc Research fr his advice and infrmatin. Financial supprt fr this wrk by the Natural Sciences and Engineering Research Cuncil f Canada (NSERC) and Cminc Research is gratefully acknwledged.

9 1 1. INTRDUCTIN Kivcet slag is prduced frm the Kivcet prcess fr lead prductin. There are tw stages in the Kivcet prcess. The first ne is an xidatin stage in which fine cal and metal sulfides in the feed bum t frm a ht sulphur dixide gas and the sulfides f lead and zinc are cnverted t xides. The xides, silica and limestne frm a semi-fused slag. In the secnd stage, the lead and zinc xides are reduced by a "cke checker", which flats n tp f the mlten slag. Lead bullin and zinc vapr are prduced. In the Kivcet smelter f Trail peratins, Teck Cminc Limited (Trail, British Clumbia, Canada), the metal xides, especially zinc xide, are nt reduced cmpletely in the secnd stage. Kivcet slag, a by-prduct f the Kivcet prcess, is an Fe(Fe )-Ca-Si02 system cntaining 15-20% zinc and 5-11% lead. Trace elements such as antimny, arsenic, indium and germanium are als fund in the slag. Generally, this zinc-bearing lead slag is treated by fuming with cal. Regardless f the fuming methd emplyed, the tail slag frm zinc fuming furnaces still cntains abut 3% zinc and sme significant amunts f lead and the trace elements. Cnventinal zinc fuming frm lead blast furnace slags cannt cntinue when zinc and lead cntents are belw wt.% and wt.% respectively, because f slid irn frmatin, which als causes the frmatin f accretins, ming f slag, and cntaminatin f the fume. 1 A new methd, electrrefining, was develped in a previus study by Fengxiang He, under the supervisin f Prfessr Ray Meadwcrft, t recver metals frm the tail slag. 2 Rbert lsn als did sme experimental wrk. 3 A series f experiments were

10 2 als cnducted in this research with tw kinds f fumer slag frm MI. The experimental data indicated that apprximately 50 percent f the zinc and mst f the lead in the slag culd be recvered by 90 minute f electrrefming. This present wrk was designed t determine what wuld happen when Kivcet slag, cntaining much higher cntents f zinc and lead than the fumer slag, is treated using the same prcesses. The slag is very similar in many respects t the fumer slag previusly tested, but because f the much higher lead and zinc cntents, its cnductance shuld be larger than that f the fumer slag. The higher cntents f Zn and Pb als make Kivcet slag mre crrsive.

11 3 2. THE SLAGS FRM MIN MIN's integrated lead-zinc smelting cmplex is lcated at Trail, British Clumbia, Canada. The cmplex is cmpsed f Zinc peratins and Lead peratins (see Fig. 1). Zinc peratins is a typical rast-leach-electrwinning prcess. Lead peratins cmprises a Kivcet flash smelter and a water-jacketed slag fuming prcess. Leach residues frm the zinc plant, as well as lead cncentrate, is treated in the Kivcet smelter and lead bullin is prduced. The slag fuming prcess is emplyed t recver zinc frm Kivcet slag, the by-prduct f the Kivcet smelter. The fume generated is cllected and returned t the zinc plant. MIN's Kivcet flash smelter and slag fuming prcess was cmpleted in 1997 and started up. The smelter has a lead capacity f 120,000 tnnes per year. In additin, zinc prductin capacity has increased t 290,000 tnnes per year frm 272,000 tnnes. The utput f tailing slag frm the slag fuming furnaces is tnnes per day. 4 ' 5> 6 ' 7 The Kivcet slag and the fumer slag in this study were water quenched at abut 1200 C t a particle size f less than 4 mm. Accrding t the cntents f zinc and lead, the tailing slag can be divided int tw types: (1) high residue fumer slag, which is under-treated in the fumer and cntains abut 4.5% zinc, and (2) lw residue fumer slag, which is ver-treated and cntains apprximately 1.5% zinc. Table 1 shws slag analysis data (average f tw separate samples f each slag) determined by IPL (Internatinal Plasma Lab Limited, Vancuver, B.C. Canada). The analyses shwn are typical f the analytical deviatin that was fund in all f the experimental wrk. It can be seen that the slags is a Fe(Fe 2 03)-Ca-Si02 system cntaining sme significant amunts f zinc and lead. Basicity (B=Ca%/(Ca%+Si02%)) f the slags is The Fe 2+ /Fe 3+ rati is abut 2.6 in Kivcet slag, 4 in high residue

12 fumer slag, and 48 in lw residue fumer slag. Trace elements such as antimny, arsenic indium and germanium are als fund in the slags. Zn Cncentrates Zn Cncentrates xygen Pressure Leach Zn Slurry Rasters iters 1 S0 2 ff gas + J Sulphite Leach Zn Calcine Pb Cncentrates S0 2 ff gas t Residues -W Kivcet Smelter Spent Electrlyte Purificatin 1 Zn Electrlyte Electrlysis 1 Melting Spent Electrlyte Fumes Fume Leach Leached Fume Kivcet Slag 7 Slag Fuming Fumer Slag Bullin Drssing Plant i Zn & Allys xide Leach Cadmium Plant Lead Refinery In & Ge Plants Ph & Allys Fig. 1: The flw sheet f the Cminc's integrated zinc-lead peratins

13 5 Table 1: Analysis f the slags frm Cminc Slag Type Zn (%) Pb (%) Sb (ppm) As (ppm) Ge (ppm) In (ppm) Cu (ppm) Fe 2+ (%) Fe 3+ (%) Si0 2 (%) Ca (%) KIV HRFS LRFS < A (%) Legend: KIV-Kivcet slag, HRFS-High residue fumer slag, LRFS-Lw residue fumer slag High residue fumer slag was characterized using SEM, EDX and XRD in a previus study. 2 The results indicated that the slag particles were hetergeneus and the maximum dimensin f mst f them was less than 3 mm. The particles were very prus because f the waterquench peratin. The slag was in a glassy state. Mst f the irn was in the slag matrix as ferrus irn. Sme f the irn existed in dendritic magnetite. There was als a little irn present as ally. Kivcet slag is very similar t fumer slag in many respects. But, because f the much higher lead and zinc cntents, the cnductance f Kivcet slag shuld be larger than that f fumer slag. The higher cntents f Zn and Pb als make Kivcet slag smewhat mre crrsive. Since the slag had been in cntact with lead bullin and cke in the Kivcet smelter, an attempt was made t determine if the Kivcet slag sample cntained metallic lead and carbn. Scanning Electrn Micrscpy (SEM) analysis indicated that there were numerus bright spts in mst f the slag particles. Black spts and cracks were als fund. Fig. 2 shws a SEM image f a slag particle that cntains a number f bright spts, a black spt and sme

14 6 cracks. A SEM image f a bright spt is shwn in Fig. 3. Tw bright spts were analyzed with EDX. The results shwn in Fig. 4 and Fig. 5 indicated that the bright spts cntained abut 80% lead with sme arsenic, antimny, zinc, irn and cpper, cmpared t a matrix reading f frm 1.5% t 12% lead. Althugh the analysis f the bright spts culd indicate lead xide, FACT 8 analysis suggests that any metal xide wuld be present as the silicate in this very acidic slag. The bright spts are assumed therefre t be metallic lead ally cntaining small amunts f the ther metals. Previus analytical wrk at Cminc suggests that up t half f the lead in the slag is present as metallic lead. 7 Fig. 6 shws a SEM image f a black spt. EDX analysis shwn in Fig. 7, Fig. 8, Fig. 9 and Fig. 10 indicated that the black spt cntained abut 98% carbn and sme zinc, lead, cpper and irn.

15 Fig. 2: SEM image f a Kivcet slag particle

16 Fig. 3: SEM image f a bright spt

17 xygen Silicn Sulfur Irn Cpper Zinc Germanium Arsenic Antimny Lead Cncentratin 9.67 wt% 0.13 wt% 0.00 wt% 1.28 wt% 0.00 wt% 2.66 wt% 2.80 wt% 2.26 wt% 0.97 wt% wt% Fig. 4: EDX analysis f ne bright spt

18 xygen Sulfur Calcium Irn Cpper Zinc Arsenic Antimny Lead Cncentratin wf% 0.00 wf% 0.25 wt% 1.52 wt% 1.25 wt% 2.68 wt% 3.43 wt% 6.27 wt% wt% Fig. 5: EDX analysis f anther bright spt

19 Fig. 6: SEM image f a black spt

20 Carbn xygen Silicn Calcium Irn Zinc Lead Cncentratin wt% 0.67 wt% 0.02 wt% 0.06 wt% 0.22 wt% 0.21 wt% 0.51 wt% Fig. 7: verall analysis f the black spt (with EDX)

21 xygen Silicn Sulfur Calcium Irn Cpper Zinc Lead Cncentratin 1.68 wt% 0.40 wt% 0.00 wt% 4.02 wt% wt% wt% wt% wt% Fig. 8: EDX analysis f Area-1 in the black spt

22 14 Carbn xygen Silicn Sulfur Calcium Irn Zinc Mlybdenum Lead Cncentratin wt% 0.32 wt% 0.00 wt% 0.00 wt% 0.01 wt% 0.03 wt% 0.04 wt% 0.00 wt% 0.10 wt% Fig. 9: EDX analysis f Area-2 in the black spt

23 15 Carbn xygen Silicn Sulfur Calcium Irn Cpper Zinc Lead Cncentratin wt% 0.15 wt% 0.00 wt% 0.00 wt% 0.00 wt% 0.02 wt% 0.07 wt% 0.02 wt% 0.04 wt% Fig. 10: EDX analysis f Area-3 in the black spt

24 16 3. LITERATURE REVIEW 3.1. THE KIVCET PRCESS The Kivcet prcess, als called the xygen Flash Cyclne Electr Thermal Prcess, was develped by VNIITSVETMET Institute in Ust-Kamengrsk. Kazakhstan, under the supervisin f Prfessr A. Sychev. The first cmmercial Kivcet unit was installed and perated at the Ust-Kamengrsk Lead-Zinc Cmbinate (nw Kazzinc J. St. C.) in There are tw stages in the Kivcet prcess. In the first stage, lead sulphide cncentrate, zinc plant residues, recycle dust, silica, limestne, fine cal and mderately carse cke are injected at the tp f the reactin shaft alng with xygen. The sulfides f lead, zinc and ther metals are cnverted t metal xides while heating in a fine cal flame. The xides, silica and limestne frm a semi-fused slag, while the gas reaches up t 15% sulphur dixide. Reactins in this stage are as fllws: C(s) (g)-c0 2 (g) C(s) + l/20 2 (g) = (g) S (g) = S0 2 (g) PbS + 3/20 2 (g) = Pb + S0 2 (g) ZnS + 3/20 2 (g) - Zn + S0 2 (g) PbS + 2Pb - 3Pb + S0 2 (g) In the secnd stage, the lead and zinc xides are reduced by a "cke checker", which flats n tp f the mlten slag. The lead xide is cnverted t metal as bullin and zinc gas is

25 17 prduced. The fllwing reactins ccur: Pb + C = Pb + (g) Pb + (g) = Pb + C0 2 (g) Zn + C = Zn(g) + (g) Zn + (g) = Zn(g) + C0 2 (g) C + C0 2 (g) = 2(g) The bullin passes thrugh the mlten slag layer under the cke checker and enters the electrthermal settler tgether with the zinc-bearing slag. In the electrthermal settler,, the heat frm the graphite electrdes keeps the bullin-slag bath in a mlten state. The lighter slag cntinues t flat t the surce and the heavier bullin sinks t the bttm f the settler. This separatin enables them t be tapped separately frm the furnace. The bullin prduced in the Kivcet furnace is treated further t remve cpper, arsenic and antimny. It is then ready fr electr-refining. The slag frm the Kivcet furnace is treated in a slag fuming furnace where the zinc in the slag vaprizes t frm a zinc xide fume, which is further treated in a xide leaching plant t recver the zinc, indium, germanium and cadmium. The ht sulphur dixide gas (abut 1200 C) frm the reactin shaft is cled in the waste heat bilers and then passes thrugh the electrstatic precipitatr. The final cleaned sulphur dixide gas is piped t sulphuric acid plants.

26 THER PYRMETALLURGICAL LEAD AND ZINC PRCESSES ther pyrmetallurgical lead and zinc prcesses include the lead blast furnace (LBF) prcess, 10 the Imperial Smelting Prcess (ISP), 11 and the QSL prcess. 12 The lead blast furnace is similar t the blast furnace fr irn prductin. Slid sinter, heated cke and refinery skims are fed at the tp f the furnace. Preheated air is blwn in at the bttm. Mlten lead and slag are tapped frm the blast furnace int a settler where they are separated. Chemical cmpsitin f lead blast furnace slag is shwn in Table In the Imperial Smelting Prcess, the charge is a mixture f cld r warm sinter and ht cke. Mlten lead and zinc vapr are prduced. The zinc vapr is cllected with cndensers cntaining a liquid lead pl. Table 3 1 shws the cmpsitin f the slag frm the Imperial Smelting Prcess. The QSL smelter can be used t treat a wide range f lead-bearing materials, such as cncentrates, battery paste, slag, Pb/Ag residues, scrap and lead glasses. The main prduct is lead bullin. The final slag is irn silicate cntaining abut 2% lead. The slags frm the abve prcesses are very similar t the Kivcet slag. If these slags are treated with the methds in this study, the results shuld be similar t that f the Kivcet slag treatment.

27 19 Table 2: Analysis f typical LBF slag Element Cntent (wt%) Si Ca 15.0 A Mg 5.0 Pb 2.2 Zn 6.0 Fe 24.0 Cu 0.3 Table 3: Analysis f typical ISP slag Element Cntent (wt%) Fe Si A Zn 5-10 Pb S 1~3

28 PYRMETALLURGICAL PRCESSES FR ZINC-BEARING SLAGS AND RESIDUES Zinc-bearing slag frm nn-ferrus smelters, such as lead blast furnaces and Kivcet smelters, is usually treated by a fuming prcess because bth melting and biling temperatures f zinc are very lw, nly C and 907 C respectively. In additin, lead melts at 327 C and bils at 1740 C. The earliest experimental wrk n slag fuming was cnducted in Australia by the Sulphide Crpratin at Cckle Creek between 1906 and Cmmercial develpment f the prcess was made by the Anacnda Cpper Mining Cmpany and the Cnslidated Mining and Smelting C. in the 1920's. 14 ' 15 The first slag-fuming furnace was installed at East Helena, U.S.A. in 1927 by the Anacnda Cpper Mining Cmpany. At present, there are many cmmercial slag fuming prcesses in the wrld such as Waterjacketed fuming prcess, 16 ' 17 ' 18 Envirplas prcess, 19 ' 20 Ausmelt prcess, 19 and Waelz kiln fuming prcess. 21 In all the abve prcesses, carbn r cal is used as reductant. Zinc and lead xides are reduced t metallic zinc and lead, which vaprize t fume. The main difference amng the abve prcesses lies in heat transfer and furnace structure. Detailed infrmatin n the abve slag fuming prcesses has been described in Fengxiang He's thesis. 2

29 PRPERTIES F ZINC-LEAD SLAGS Activities f Zn and Fe in Zinc-bearing Slags Many researchers have studied activities f Zn and Fe in zinc-bearing slag with several methds. 22 ' 23 ' 24 25, 26 ' Studies als have been dne n the activity f zinc in the mlten Cu-Zn- Fe ternary system, activity measurements in liquid Cu-Zn-X (X = Pb, Ag, and Au) ternary allys and the equilibrium between Ca-Si0 2 -Fe x slag and Cu-Zn-Fe (irn-saturated) ally. 27,28 r e s ui t s 0 f these studies have been described in Fengxiang He's thesis. 2 In summary, the activity cefficient f Zn in Ca-Si02-"Fe" slag increases with increasing slag basicity (%Ca/(%Ca+% Si0 2 ). It is nearly independent f zinc cncentratin. When irn xides and zinc xide cexist in the slag, the activity cefficient f Fe depends n the mle fractins in the slag. It als increases with increasing slag basicity. Fr zinc blast furnace slag, Fe starts t be reduced when the cncentratin f Zn is less than 3 ml%. 1

30 Cnductivity f Zinc-Lead Slags Cnductivity f zinc-lead slags is related clsely t the specific cnductivities f pure xides and the inic nature f the Fe-Ca-Si0 2 system. It has been described in Fengxiang He's thesis. The results are summarized here. The xides can be divided int cvalent and inic grups. The imprtant cvalent xides include Si0 2, Ge0 2, B 2 0 3, P and As In these xides, xygen is bnded s as t frm three-dimensinal netwrks. In the liquid state, these xides have very high viscsities f 10 5 ~10 7 cp and very lw specific cnductances f 10" 5 ~10" 6 hm"'cm' 1. The remaining metal xides are mre r less inic. When liquid, they have viscsities f cp and specific cnductances greater than 10 hm''cm' 1. Table 4 29 ' 30 shws specific cnductances f sme xides near their melting pints. Table 4: Specific cnductances f sme xides near their melting pints xide Fe Cr Ca Mg A Zr0 2 Ti0 2 Pb Si0 2 Melting pint ( C) Specific cnductance (hm"'cm' 1 ) " s The inic nature f the "Fe"-Ca-Si0 2 system with Ca/(Ca+Si0 2 ) ratis f has been studied by Dicksn and Dismukes. 31 The system cnducts current by bth inic and nninic mechanisms. Inic cnductance increases with increasing silica cntent. When Fe cncentratin is increased, bth inic and nninic cnductances increase. The increase in

31 23 inic cnductance is cnsistent with the increase in cncentratin f catins and inic mbilities. The reasn fr the increase in nninic cnductance is p-type semi-cnductin. Ande current efficiency increases with decreasing Fe cntent because f the electrical cnductin reactins (Fe ++ - e = Fe +++ at the ande and Fe e = Fe ++ at the cathde). When Fe cncentratin is less than 40wt%, ande current efficiency is mre than 90%. It des nt vary with temperature by any significant degree and gives a realistic measure f the degree f inic cnductance because the amunt f xygen gas prduced at the ande is crrespnded t the amunt f metal prduced at the cathde. Accrding t the abve results n the specific cnductivities f pure xides and the inic nature f the Fe-Ca-Si02 system, the ttal electrical cnductances f the fumer slag and the Kivcet slag in this study are estimated t be apprximately 0.5 hn-f'cm" 1 and 2.6 hm" 'cm' 1 respectively. The Kivcet slag has a higher electrical cnductance because it cntains higher cntents f zinc and lead xides. The inic cnductances in the three slags accunt fr mre than 90%.

32 THE HALL-HERULT PRCESS Carbn is usually used as reductant in pyrmetallurgical prcesses fr metal prductin. But aluminum cannt be prduced by this methd. When alumina reacts with carbn, AI44C, but nt Al, is the primary prduct. All f the fllwing reactins might ccur: 2AI23 + 3C = AI44C + 2(g) AI44C + 6C = AI4C3 + 4(g) A C = Al 2 0(g) + 2(g) Al C = 2Al(g) + 3(g) A C + C = 2Al 2 0(g) + 2(g) A C + 3C = 4Al(g) + 4(g) H. Davy was the first persn wh attempted t decmpse alumina electrlytically. 32 In 1807, he melted it with current frm a battery. Sme aluminum was reduced, but it allyed with the irn leads. R. W. Bunsen and S. C. Deville prduced aluminum electrlytically by using fused sdium-aluminum chlride, but it was nt a practical prcess. The aluminum chlride was cntinually used up. It als vlatilized frm the mlten salt. This resulted in an increase f sdium chlride cntent and thus raised the melting pint f the electrlyte. Increasing the electrlyte temperature increased the vlatilizatin lsses. Charles Martin Hall successfully slved the prblem. n February 23, 1886, he electrlyzed a slutin f alumina in mlten crylite (Na3AlF 6 ) and prduced shining glbules f aluminum at his hme. 32 The key f his inventin was the discvery f a fused electrlyte which disslved alumina in substantial quantities and pssessed a higher stability than the alumina.

33 25 In additin, his technique had ther advantages such as a reasnably lw melting pint, a lw perating vltage f abut 6 vlts, and a specific gravity lw enugh t permit pure aluminum t sink thrugh the electrlyte and be prtected. Paul L. T. Herult applied fr and was granted a French patent n the electrlysis f alumina in crylite n April 23, n April 15, 1887, he gt anther French patent n a different prcess, which nly prduced aluminum allys. 32 Pure alumina in a carbn-lined furnace was fused electrthermally by heat frm an electric current. A large carbn ande was suspended in the furnace. A layer f mlten cpper in the bttm f the furnace was used as cathde. Electrlytically reduced aluminum went int the mlten cpper t frm an aluminum brnze ally. The ally culd be tapped ut f the bttm f the furnace. Cpper and alumina were added at the tp. Tw years later, Herult fund that the furnace used fr the aluminum brnze ally culd be emplyed in the alumina-crylite prcess t prduce pure alumina.

34 26 4. BJECTIVES The first purpse f this study is t recnfirm the feasibility f recvering the heavy metals Zn, Pb, In and Ge frm final zinc fumer slags by an electrrefining technique which was develped in previus study. A series f experiments was cnducted with tw types f fumer slag frm Cminc. The secnd bjective was t determine what wuld happen when Kivcet slag, cntaining much higher cntents f zinc and lead than the fumer slags, is treated using the same prcesses. Kivcet slag is very similar in many respects t the fumer slag previusly tested, but because f the much higher lead and zinc cntents, its cnductance shuld be higher than that f the fumer slag. The higher cntent f Zn and Pb als made Kivcet slag mre crrsive.

35 27 5. FACT CALCULATIN N THE KIVCET SLAG The ptential changes pssible in this system were examined using thermdynamic calculatins made with FACT sftware 8. Table 5 shws the calculatin results n 250 grams f Kivcet slag. Half f the lead in the riginal slag was assumed t be metallic. Carbn cntent was assumed t be 0.23%, a value which was derived frm sme f the subsequent experimental data. At 1250 C, when the system pressure was set t 1 atmsphere, all f the carbn was cnverted t 0.21 grams f and 1.80 grams f C0 2 at equilibrium, resulting in a pressure f atmspheres and ac0 2 pressure f atmspheres. Abut 0.19 grams f zinc and 0.32 grams f lead were als fund in the gas phase, giving a zinc pressure f atmspheres and lead pressure f atmspheres. The activities f Zn and Pb in the slag were and respectively. The metallic lead in the slag increased frm grams t grams, indicating that very little vaprizatin f the liquid lead ccurred and sme lead xide was reduced t liquid lead. The amunt f Fe increased frm grams t grams, while the weight f Fe^ decreased frm grams t grams. Sme Fe 2 03 was reduced t Fe. Althugh the Fe/Fe weight rati was nly abut 5.4 at equilibrium, the rati f Fe activity (0.498) t Fe activity (0.014) was as high as 35.6, giving the divalent irn in a reasnable reductin ptential. These results suggest that there is cnsiderable ptential fr the further lss f zinc and lead t the gas phase.

36 28 Table 5: Results f FACT calculatin n the Kivcet slag 25()g Kivcet Slag + Ar Gas phase Liquid Slag Liquid Lead Ar Zn Pb C02 Zn Pb Fe Fe Cu 2 0 Pb Zn Fe Cu gram gram gram gram gram activity activity activity activity activity gram gram gram gram g Kivcet Slag + 200g Ar + lg Crucible Gas phase Liquid Slag Liquid Lead Ar Zn Pb C02 Zn Pb Fe Fe Cu 2 0 Pb Zn Fe Cu gram gram gram gram gram activity activity activity activity activity gram gram gram gram g Kivcet Slag + 200g Ar + lg Crucible + 150g Cpper Gas phase Liquid Slag Liquid Cpper Ar Zn Pb C02 Zn Pb Fe Fe Cu 2 0 Pb Zn Fe Cu gram gram gram gram gram activity activity activity activity activity gram gram gram gram If argn was intrduced int the abve system at 1250 C, the amunt f metallic lead in the slag decreased sharply, while the weight f lead in the gas phase increased dramatically. Activities f Zn and Fe in the slag decreased, while Fe203 activity increased with the lss f Zn t the gas phase. When the amunt f argn in equilibrium with the slag was set t 200 grams, almst all f the carbn was cnverted t 2. The amunt f lead in the gas phase at grams was very clsed t that (11.55 grams) f metallic lead in the riginal slag. The amunt f Pb at equilibrium was almst equal t that in the riginal slag. The activity f

37 29 Zn drpped t and 4.83 grams f zinc went int the gas phase. At the same time, Fe activity decreased t 0.413, while Fe203 activity increased t Clearly the divalent irn in available in the slag can reduce zinc xide. If the zinc and lead in the gas phase are remved cntinually, sme zinc and lead in the slag can be recvered just by hlding at temperature. When a FACT analysis was dne f slag heated t 1250 C in a fireclay crucible (36% A and 57% Si02), 100 grams f the crucible were assumed t disslve int 250 grams f the slag. In this case, activities f all the abve xides decreased as the ttal weight f the slag increased. When 200 grams f argn was intrduced int the system, nly 1.15 grams f zinc and 4.31 grams f lead went int the gas phase at equilibrium. The amunt f Pb in the slag increased frm grams t grams and n metallic lead was present in the slag. The amunt f Fe increased t grams, while that f Fe203 decreased t 3.78 grams. Apparently, sme Fe was reduced by metallic lead. Althugh the Fe/Fe wt% rati increased t 17.7, the rati f Fe activity t Fe activity decreased t 12.5 because the disslved crucible increased the Fe20 3 activity cefficient frm t 1.626, while it decreased the Fe activity cefficient frm t Divalent irn ins lst sme f their reductin ptential. The activity cefficients f Zn and Pb were als decreased frm and t and respectively. The disslved crucible had significant influence n the metal recvery. n a cmmercial scale, where the surce t vlume rati f the slag is much lwer, the rati f disslved refractry in the slag shuld be much lwer and the influence will be smaller. In the FACT analysis f the abve system equilibrated with 150 grams f cpper, the amunt f zinc in the gas phase increased t 1.36 grams, while that f lead decreased t 2.99 grams.

38 30 At the same time, abut 0.53 grams f zinc and 9.19 grams f lead were recvered int the liquid cpper. The amunt f lead xide at equilibrium was very clse t that in the riginal slag. Mst f the metallic lead went int the liquid cpper. Using cpper, a greater quantity f zinc and lead can ptentially be remved frm the slag. Sme Fe203 was reduced t Fe by cpper. The weight f the cpper decreased by 6.6 grams and activity f Cu 2 0 in the slag increased frm 0 t In the case f 0.1 % Zn, Pb and Fe in a Cu-Zn-Pb-Fe melt, the rati f Fe activity t Zn activity is apparently 296. Als, the Fe activity is 15 times higher than the Pb activity. There shuld therefre be a thermdynamic driving frce fr zinc and lead t enter the liquid cpper withut much irn.

39 31 6. EXPERIMENTAL 6.1. EXPERIMENTAL APPARATUS A schematic diagram f the experimental apparatus is shwn in Fig. 11. The detailed infrmatin n the different parts f the apparatus is given belw. Pwer Supply f Temperature Current, Vltage 7 V Ar Inductin Furnace Data Acquisitin 0 00 Ampere Kw Vlt Inductin Cntrller Fig. 11: Schematic diagram f the experimental apparatus

40 32 Inductin Furnace A self-cnstructed inductin furnace (Fig. 12) was emplyed t melt the slags. A graphite bushing (labeled '13' in Fig. 12, 5'/ 4 "(.D.) x 3 3 / 4 "(I.D.) x 9"(L), supplied by Natinal Electrical Carbn Canada, Edmntn, AB, Canada) was used as the heating element f the furnace. This heating element cmbined with the Mg ring (labeled '7') and the alumina ring (labeled '14'), separated the furnace int tw chambers. The inner chamber was the place inside the graphite bushing, which was used as the wrking space fr the crucible assembly. The uter chamber was the space between the graphite bushing and the refractry bucket (labeled '5'), which served as insulatin and graphite bushing prtectin. A fireclay crucible (labeled '12') cntaining the slag was placed in a graphite cup (labeled '11') inside the inner chamber. In the cases f a leak f mlten slag, a slag verflw frm the crucible, and a melting f the crucible, the graphite cup culd hld the mlten materials t prtect the furnace. A thermcuple was placed abve the slag surce t measure the temperature. The uter chamber was filled with carse alumina pwder (labeled '6'), which was used as an insulatr. The average size f the alumina pwder was abut 2.1 mm. Argn was intrduced int the inner chamber thrugh the three jets lcated in the bttm fiber plate (labeled '8') and ne jet in the tp refractry cver (labeled '1') t prtect the bath frm xidatin and t reduce the xidatin f the graphite bushing. A secnd stream f argn was intrduced int the uter chamber thrugh anther three jets lcated in the bttm plate t prtect the graphite bushing. Flw rate f the argn streams were cntrlled with a mass flw cntrller.

41 33 In the electrreductin trials, a graphite rd (10 mm in diameter) was used as the ande immerged int the liquid slag. The graphite ande was mre mechanically stable than the platinum ring, which was used in the previus study 2 Separate runs indicated that the extent f reactin between the graphite rd and the slag when n current was applied was negligible. The cathde is a liquid cpper melt with a M electrde (0.8 mm in diameter), sheathed in alumina except where immersed in the cpper. FACT 8 calculatin indicated that in the case f 0.1 % zinc, lead and irn in a cpper melt at 1250 C, irn activity was abut 296 times and 15 times higher than zinc and lead activities respectively. In additin, at this temperature the slubility f M in Cu is negligible and n wear f the M electrde was nticed in any f the trials. The electrdes were placed t the desired psitin with a XYZ Mvement Cntrller. A cmputer-based data acquisitin system (supplied by Keithley Instruments, Data Acquisitin Divisin, Tauntn, MA, USA) was emplyed t recrd vltage and current readings frm the DC pwer supply. The data acquisitin card culd btain data at different frequency and saved it in an ASCII frmat. This frmat data culd be imprted int Excel spreadsheets. At the end f the experiment, a graphite shaft was used t push the graphite cup hlding the crucible t the furnace tp s that it culd be remved frm the furnace.

42 34 C mputer Data Acquisitin System Fig. 12: Inductin furnace (1) furnace cver, (2) tp plate, (3) side supprt stands, (4) inductin cils, (5) refractry bucket, (6) carse alumina pwder, (7) Mg ring, (8) bttm plate, (9) argn inlet tubes, (10) graphite shaft, (11) graphite cup, (12) fireclay crucible, (13) graphite bushing, (14) alumina ring

43 35 Crucible The crucible used was a fireclay material analyzing 36% AI23 and 57% SiC>2 with Fe2C>3 and TiC»2 as the majr cntaminants. This cmpsitin shuld be almst exactly half mullite (Al 2 03.Si0 2 ) and half silica. This material was chsen after trying a variety f refractry materials in the previus study n fumer slag. The slag is acidic, with a Ca/SiC»2 rati less than 1, but it is nt saturated with either Si0 2 r AI23. Cnsequently, the slag disslves any basic refractry within minutes but als attacks expensive quartz r alumina refractries very substantially. The cheaper fireclay used was als attacked by the fumer slag, but n mre than alumina r quartz. Kivcet slag is similar t the fumer slag in this respect, but is mre crrsive due t higher Zn and Pb cntents. In the analysis f results, the change in slag cmpsitin because f crucible ersin is cnsidered and discussed. The crucible is cnical in shape, 118 mm in depth, with a diameter f 86 mm at the tp and 56 mm at the bttm (see Fig. 13).

44 86 mm < H Fig. 13: Assembly f the crucible Fume Cllectin Device A simple fume cllectin device was made t cllect fume (Fig. 14). A vacuum cleaner was used t prduce a frce. The ff-gas entered a cllectr, which was made f glass. Then it passed thrugh a filter and the particles in the gas were cllected n a filter paper (8 um).

45 Fig. 14: Schematic diagram f the fume cllectin device 37

46 METHDLGY The experiments in this study can be divided int rughly 2 categries: 1. Metal recvery frm the slags under different cnditins 2. Electrical resistance measurement Metal Recvery At first, a series f runs were cnducted with tw fumer slags t cnfirm the results f the previus study. In that study, nly limited chemical analysis had been dne and the extent f reactin with the crucible was nt apparent. This prduced results that gave an apparent greater recvery f zinc but masked the differences between the different experimental techniques used. Fr this study, Cminc vlunteered t pay fr all the chemical analyses, including a reasnably cmplete element analysis f each slag sample and the rati f Fe" t Fe +++. This permitted a much mre detailed analysis f the experimental results. The first fumer slag had a high residual cntent and reflected an inadequate prcessing in the fuming furnace. All metals f interest, zinc, lead, germanium and indium, were present at abve average levels. The secnd fumer slag had a very lw residual level, cnsiderable belw the nrmal average fr this prcess. The analyses f these initial slags are given in Table 1. The trials with the tw types f fumer slag were f three types: 1. Slag was heated at 1250 C. fr 2 hurs t determine if either zinc r lead wuld vlatilize and t determine the extent f reactin with the crucible.

47 39 2. Slag (generally 250grams) was melted with 150 grams f cpper at 1250 C t determine the extent f redistributin f Zn, Pb, In and Ge withut use f vltage and t cmpare with results btained frm FACT analysis. 3. Slag ( grams) and cpper were melted and subjected t a vltage f 5 vlts t determine if the cleaning f Zn, Pb, In and Ge frm the slag was enhanced. Next, Kivcet slag was treated using the same prcesses t see what wuld happen. Analysis f the riginal Kivcet slag is als shwn in Table 1. As mentined abve, Kivcet slag is mre crrsive than fumer slag. When substantial quantities f Kivcet slag were melted, it was necessary t add sme amunt f grund crucible t the starting slag pwder t prevent the slag frm eating thrugh the crucible wall. The runs using the Kivcet slag can be divided int the fllwing grups: Melting Kivcet slag (250 r 500 grams) at 1250 C fr 2 hurs t see if either zinc r lead culd be recvered withut using a reductant. Melting a charge-mixture (250 grams f Kivcet slag + 25 grams f crucible pwder) at 1250 C fr 90 minutes t determine hw much zinc and lead can be recvered. Equilibrating 275 grams f the charge-mixture with 150 grams f cpper at 1250 C fr 90 minutes t define the distributin f the recvered Zn and Pb. Melting the charge-mixture and cpper at 1250 C with 5 vlts applied t determine if metal recveries wuld be enhanced. In an attempt t simulate a cunter flw prcess, Kivcet slag was treated t remve sme f the zinc and the lead and then was electr-refined with new

48 40 cpper three times t determine the zinc and lead cntents that culd be reached. In all experiments, the slag temperature was 1250 t 1270 C with abut a C temperature difference between the slag and the thermcuple. Hlding time at this temperature was 90 r 120 minutes. A slag sample was taken with a steel rd every 15 t 30 minutes. A fume sample was cllected in sme runs. A sample f the cpper buttn was nly taken after the run was finished and the slag was cled t rm temperature. The slag samples, the fume samples and the cpper buttns were sent t IPL fr chemical analysis.

49 Electrical Resistance Measurement Firstly, a series f experiments were cnducted t measure the electrical resistances f the liquid slags. As shwn in Fig. 15, tw graphite rds (10 mm in diameter) were immerged int the liquid slag at 1250 C. The distance between the graphite rds was 2 cm. A vltage f abut 1.4 vlts was applied acrss the graphite rds fr abutl minutes. Then the distance between the graphite electrdes was increased t 4 cm. The same vltage was applied fr 10 minutes again. After that, the graphite rds were lifted ut f the liquid slag and their tips cntacted each ther fr 10 minutes with the same applied vltage. The vltage and the current in each step were recrded with the cmputer-based data acquisitin system. Next, the resistance f liquid cpper at 1250 C was measured with a similar methd t that in the slag resistance measurement. The graphite rds were replaced by tw pieces f mlybdenum wire (0.8 mm in diameter) sheathed in alumina except fr the part cntacting the liquid cpper (see Fig. 15). Finally, the ttal resistance in electrrefining was measured. As shwn in Fig. 16, a graphite rd was immerged int the liquid slag and used as the ande. The tip f the graphite rd was 2 cm away frm the slag-cpper interce. A mlybdenum electrde was immerged int the liquid cpper. The distance between the mlybdenum electrde tip and the slag-cpper interce was als 2 cm. A vltage f 5 vlts was applied acrss the graphite ande and the mlybdenum electrde fr abut 10 minutes. The vltage and the current were recrded with the data acquisitin system.

50 1.4 V 1.4 V Fig. 15: Schematic diagram f slag and cpper resistance measurement

51 Fig. 16: Schematic diagram f resistance measurement in electr refining

52 44 7. RESULTS AND DISCUSSIN 7.1. METAL REVERY Metal Recvery frm the Fumer Slags Tw types f fumer slag, high residual and lw residual, were treated in the experiments. During all the runs, there was a reactin between the slag and the crucible that appeared t reach equilibrium after abut ne hur r less. Fig. 17 shws the change in Ca and Si0 2 cntents f the slag with time in slag reheating with n cpper. The rate f change is decreasing with time. It is pssible by using the Ca analysis t calculate the weight f the final slag. Fig. 18 indicates that an initial 250 grams f slag reaches a irly unifrm weight f 320 grams after ver tw hurs f prcessing at temperature. The exact dilutin ctr was cnsidered in all calculatins f metal lss frm the slag during prcessing. The mst imprtant aspect f the crucible disslutin is the impact f the higher silica and alumina n the activity f the zinc and lead xide in the slag. The FACT sftware suggests that the initial slag has a Zn and Pb activity f and respectively. After disslutin f the crucible t the values nted, these activities have been reduced t and , a reductin f almst exactly fifty percent. Since the change in slag cmpsitin in an industrial system, with a much lwer surce t vlume rati, wuld be much lwer, it might be expected that the results reprted belw represent a wrst case scenari.

53 45% r U a 40% - 35% - 30% 1 1 IL c««*- 25% - v= 0 s 20% jr -A I A 1 Si02: High residual Si02: High residual Si02: Lw residual A Si02: Lw residual Ca: High residual Ca: High residual Ca: Lw residual A Ca: Lw residual 15% - 10% - 4- Melt in Time in minutes at 1250 C 120 Fig. 17: The change in Ca and Si02 cntents f fumer slags with time 400 6D W CS n * * -j - i : 2 s - High residual fumer slag High residual fumer slag Lw residual fumer slag _ A Lw residual fumer slag Melt in Time in minutes at 1250 C Fig. 18: Increase in the weight f fumer slags with time

54 46 Slag remelting with n cpper A number f runs were cnducted at 1250 C using 250 grams f fumer slag melted in a fireclay crucible. As sn as the slag melted, there was a substantial display f fume and the analysis f the slag altered cnsiderable ver a tw hur perid as shwn in Fig. 19, that gives the apparent slag cmpsitin with time f duplicate runs with the high residual fumer slag. This graph is misleading in that it ignres the dilutin effect f the crucible ersin. The actual percentage f the riginal zinc and lead that are remved is shwn in Fig. 20, where this ctr is cnsidered. Surprisingly, rughly thirty percent f the zinc and fifty percent f the lead have been remved simply by allwing the slag t equilibrate at temperature. In these runs, the cmbined weight f zinc and lead vaprized frm 250 grams f slag is calculated at rughly 4.2 grams. The weight lss f the slag and crucible, after crrecting fr sample weights, was 5.5 and 7.1 grams fr the tw runs shwn. The fume cllected frm these runs, see Table 6, was a mixture f very white crystals with a yellw tinge, and small black glass particles. The latter were clearly small slag particles ejected int the gas phase during melting. The verall analysis f the fume indicated abut percent slag and ver 80 percent lead and zinc xides in rughly equal amunts. It shuld be nted that the Ge and In analyses f the fume were rughly 200 and 400 ppm respectively, indicating a recvery f these elements t the fume f ver 10 percent.

55 47 c at s a TJ ca TJ c ca u c N -Wt%fZn -Wt%fZn Q Wt%f Pb... wt%f Pb Meltin Time in munutes at 1250 C Fig. 19: Analysis f Zn and Pb in the high residual fumer slag, uncrrected.q Q. T3 > 8> Melt Time in minutes at 1250 C Fig.20: Zinc and lead lss by slag reheating-high residual

56 48 Table 6: Fume analysis - Fumer slag Slag type Cnditin Zn% Pb% Ge ppm In ppm High After heating Residual After heating with Cu Lw Residual After heating When the lw residual fumer slag was remelted, the lead remval was near zer and the zinc remval ver 30 percent as shwn in Fig. 21. The lw lead remval is nt surprising since the riginal cntent f lead in this slag was just ver 0.03 percent. It is interesting t nte that even thugh the zinc cntent in this slag is ne-third that f the high residual fumer slag, the zinc remval is still substantial. The weight lss f the slag and crucible in these runs was lwer than the high residual runs, being 1.9 and 3.6 grams fr the duplicate runs. In the fume, the zinc t lead rati was rughly 3/1 and these tw materials represented just ver half f the fume. The initial analysis fr In and Ge was very lw in this slag and it appeared that all f these metals reprted t the fume. Hwever, at the ppm level, the analysis is nt reliable enugh t calculate the percent remval. In the slag, the divalent irn in is the nly reductant present in a substantial amunt. The reactins 2Fe ++ + Zn ++ = 2Fe Zn(gas) and 2Fe ++ + Pb ++ = 2Fe Pb(gas)

57 49 appear t take place readily in the first thirty minutes f melting. Analysis f the high residual fumer slag using FACT indicates that the pressure f Zn ver the slag at melt-in shuld be atmspheres and the pressure f Pb, atmspheres. These values drp t and respectively after crucible disslutin. Given the extent f the fume and the high lss f lead and zinc, these calculated values wuld appear t be a trifle lw. 70% 60% N 50% 75 40% > _ 30% 2. v 20% 10% 0% Zn recvery Zn recvery _ Melt in Time in minutes at 1250 C Fig.21: Zinc lss by slag reheating -Lw residual Since in the reductin f lead and zinc frm the slag the electrical charge balance must be maintained, a calculatin was made f the gram-in equivalents f the majr inized species, zinc, lead, cpper, and irn, bth divalent and trivalent. The balance, shwn in Table 7, was generally cnsistent, but the variability was high. The analysis fr divalent and trivalent irn appears t be ne f the less reliable nes and scatter in the results is quite large which is unfrtunate when divalent irn is the majr reductant in the slag. (An analysis was dne n the initial slags t determine if there was residual carbn frm the fuming prcess. The amunt fund was under 0.05 percent.)

58 50 Table 7: In equivalents in the fumer slags Slag type Cnditins Cu Zn Pb Fe I*t/96487 Sum As received High After heating Residual After heating with Cu After electrreductin As received Lw After heating Residual After heating with Cu After electrreductin Slag remelting with cpper with n current applied A series f runs were made at 1250 C with n current applied using 250 grams f fumer slag with 150 grams f cpper. The zinc and lead lss frm the high residual fumer slag, shwn in Fig. 22, indicates clearly the cmbined effect f fuming f the slag and the remval f zinc t the cpper. After rughly sixty minutes, a relatively cnstant value appears t have been reached. At the end f the tw runs shwn, between 20 and 30 per cent f the zinc had been remved frm the slag and ver 80 percent f the lead. Had all f this zinc and lead reprted t the cpper, the cpper shuld analyze 1.78 per cent zinc and 1.50 percent lead. The analysis f the cpper is shwn in Table 8. It is seen that the actual analyses fr zinc and lead are rughly 0.3 and 1.0 percent respectively with an irn cntent f 0.11 percent. It wuld appear that rughly 80 percent f the zinc lst and 30 percent f the lead lst, r rughly 3.8

59 51 grams f metals, have reprted t the fume. The actual weight lss t the fume in these runs averaged 3.5 grams with zinc and lead in the fume analyzing in the rati f 2.5 t 1 (Table 6). Cnsidering the vagaries f the analysis, the agreement is very gd. The cpper analysis f the slag after equilibratin increased t 0.69 percent frm 0.38 percent. It can be seen that a small fractin f the indium reprts t the cpper in the high residual fumer slag case. Hwever, the majrity f bth the indium and germanium reprt t the fume. 1 D_ tf is w CC I 90% 80% 70% 60% 50% 40% 30% SI) 20% 10% 0% - Zn recvery - - Zn recvery - -g - - Pb recvery -- - Pb recvery Melt in Time in minutes at 1250 C 90 Fig. 22: Zinc and lead lss with cpper getter-high residual

60 52 Table 8: Cpper buttn analysis - Fumer slag Cpper buttn cmpsitin Slag type Cnditin Zn% Pb % Fe% Ge ppm In ppm High After heating with Cu <5 73 Residual After electrreductin <5 59 Lw After heating with Cu Residual After electrreductin <5 Analysis f this system using FACT is difficult since the equilibrium vlume f gas passing ver the system is difficult t estimate. Hwever, ignring the gas phase, FACT suggests that the zinc, lead and irn cntent f the cpper wuld be 0.10, 0.81 and weight percent respectively and that the cpper cntent f the final slag wuld be 2 percent. Hwever, the zinc and lead vapr pressures wuld be the same as calculated fr the n cpper case and there wuld bviusly be a significant lss f these metals t the fume. These calculated values are all substantially lwer than the actual recveries, indicating that the reductin ptential in the system is greater than indicated by the apparent Fe ++ /Fe +++ rati. Hwever, the actual electrical equivalence in Table 7 shws a reasnable balance. FACT calculatin indicated that at 1250 C the activity cefficients fr irn and zinc at infinite dilutin in the cpper melt were 19.9 and respectively. Using the frmula Zn(in Cu) + Fe(in slag) - Fe(in Cu) + Zn(in slag), it can be calculated that the rati f zinc t irn in the cpper shuld be:

61 53 ^ = 28.5^ %Fe a P, n If the activity cefficients f the xides are assumed t be equal, the rati f zinc t irn in the cpper fr this slag shuld be 3.9. Using the activity cefficients fr Zn and Fe frm the FACT sftware fr this slag cmpsitin (0.326 and respectively), the rati shuld be The actual rati, frm Table 8, is 3.1. Runs made with the lw residual fumer slag als shwed a substantial remval f zinc, in the rder f 50 percent, as seen in Fig.23. The initial lead cntent was very lw (0.03%) but the final lead cntent als appeared t be lwered t abut 0.01 percent. f the rughly 1.8 grams f zinc that was remved frm the slag (average f tw runs), sme 0.65 grams was recvered in the cpper and ver 1 gram was remved in the fume. This crrespnds t the verall weight lss in the experiments. Cpper lss t the slag was very lw. Melt in Time in minutes at 1250 C Fig.23: Zinc and lead lss with cpper getter-lw residual

62 54 Analysis f this system using FACT 8 suggested that, ignring the gas phase, the cpper wuld analyze 0.05 percent zinc and 0.02 percent irn and that the slag wuld increase t 1.6% Cu. Again the actual results wuld appear t indicate that the cnditins in the experimental furnace are cnsiderably mre reducing than indicated by the initial Fe ++ /Fe ++ " rati. Hwever, in this case, the in equivalent balance (Table 7) is nt gd and it appears that a high percentage f divalent irn has been xidized with very little material apparently being reduced. Slag Remelting with Cpper with 5 vlts Applied In this series f runs, 5 vlts was applied acrss the electrdes shwn in Fig. 12 and the results were cllected as in the previus series. A typical curve f current and vltage versus time is shwn in Fig. 24. In all cases, after a very brief lag, the current reached a high pint and then slwly decreased, presumably as the mbile ins in the slag were depleted. The curve fr zinc lss in the high residual fumer slag is cmpared t zinc lss with n vltage in Fig. 25. After the initial melt in, it is seen that the zinc lss is greater at all times fr the case in which current is applied. In this case, a sample was als taken f the slag after the crucible and slag had cled in cntact with the cpper. As seen, there was a marked reversin f zinc int the slag after the vltage was remved, indicating that the vltage had indeed created a new equilibrium. The irn and zinc cntents f the cpper buttns recvered after the runs were much higher than thse frm the runs with n vltage and the ratis f zinc t irn were much lwer. The lead cntent f the cpper was lwer with vltage applied, even thugh the lead remval frm the slag was marginally higher with vltage applied as seen in Fig. 26. The electrical equivalence f the slag after treatment is seen in Table 7 where the cntributin

63 55 f current times time has been cnsidered alng with the valence change f the elements. It appears that the cntributin f the applied vltage is significant but nt as impressive as hped. 6.0 j- 5.5 I Time in minutes Fig. 24: Typical Current-Vltage-Time recrd Time in minutes at 1250 C Fig. 25: Cmparisn f zinc recveries - High residual electrreductin

64 56 (8 > E Melt in Final slag Time in minutes at 1250 C Fig. 26: Cmparisn f lead recveries - High residual electrreductin Electrreductin f the lw residual fumer slag didn't give a psitive benefit. The lss f zinc frm the slag, shwn in Fig. 27, was perhaps marginally imprved but the difference is certainly within the limits f analysis. Fig. 27: Cmparisn f zinc recveries - Lw residual electrreductin

65 57 Cnsidering the culmbs passed in the electrreductin f the tw slags, it can be calculated that the current efficiency fr the high residual fumer slag case was 95.6 percent and fr the lw residual case was 90.1 percent. This is very similar t the values predicted by Dicksn and Dismukes 31 fr slags with a lw basicity. Cmparisn f the results in this study and in previus study Table 9 shws the zinc cntent in the high residual fumer slag befre and after 90 minutes f treatment in this study and in the previus study. Zinc cncentratin drpped t % after melting with and withut cpper in this study. This agrees with the result f abut 2.5% in the previus study. Hwever, wt% f zinc decreased t a lwer level f 1.93% after electr refining 90 minutes in this study. Actual zinc recvery (abut 47%) was higher than thse (20~35%) in the runs with n current applied, indicating that the current enhanced the remval f zinc frm the slag. In the previus study the effect f the current n zinc recvery frm the high residual fumer slag was nt clear. A pssible reasn was that the slag analysis was nt accurate enugh. Hwever, in the case f a synthetic slag (Slagl, Zn%=4.33) in the previus study 2, a vltage f 5 vlts decreased the zinc cntent t a lwer level (abut 0.8%) than thse ( %) with n vltage applied. Table 9: Zinc cntent in high residual fumer slag befre and after treatment (90 minutes) In this study In the previus study riginal high residual fumer slag 4.5% 4.5% After melting withut Cu 2.42% Abut 2.5% After equilibrating with Cu 2.57% Abut 2.5% After electrrefining 1.93% Abut 2.5%

66 58 In the case f lw residual fumer slag in this study, abut 55% f the zinc was recvered by electrrefining. Zinc cncentratin in the slag decreased t abut 0.55% and stabilized at this level. N experiment was cnducted with lw residual fumer slag in the previus study. But in the electrreductin runs using anther synthetic slag (Slag2, Zn%=1.98), which was similar t lw residual fumer slag, it was fund that zinc culd nt be remved frm the slag when its cntent was lwered t abut 0.45%. The results in bth studies are similar. Analysis f the cpper buttns in the runs using high residual fumer slag in this study indicated that (1) with current passing, mre zinc and irn were depsited in the cpper melt than withut current applied, and the cncentratin f zinc was, nearly duble that f irn; (2) lead, germanium and indium can als be cllected in the cpper melt, and there was n significant difference fr their cncentratin in the cases with and withut current passing (Table 8). This agrees well with the result in the previus study. In the runs using lw residual fumer slag in this study, the current als enhanced the thermdynamic driving frce fr remval f zinc and irn t the cpper melt. Hwever, irn cntent was much higher than that f zinc because the wt% f zinc in the slag was quite lw. Fume was bserved in all runs in bth studies. The main cntents f the fume were zinc and lead xides in rughly equal amunts. Cncentratins f germanium and indium in the fume were much higher than thse in the slag. In the electrrefining runs in bth studies, vltage increased slightly during the whle melting perid, while current increased a little in the first several minutes and then decreased slwly. In this study, current efficiency was calculated based n the difference in the ttal in equivalents f zinc, lead, irn (divalent and trivalent) and cpper in the slag befre and after

67 59 treatment. The calculatin results f mre than 90% was higher than that (68%) in the previus study, in which the current efficiency was calculated accrding t the zinc cncentratin difference in the slag and the irn cncentratin difference in the cpper befre and after treatment.

68 Metal Recvery frm the Kivcet Slag Melting Kivcet Slag A series f runs was cnducted using different amunts f slag. The slag disslved sme f the silica and alumina in the fireclay crucible at high temperature. In the case f 250 grams f riginal slag, silica cntent in the slag increased t 34.6% (average f tw runs, see Fig. 28) after 120 minutes. At the same time, Ca cncentratin decreased t 10.2% and slag basicity drpped t The amunt f Ca in the slag was assumed t be stable. Slag weight calculatins based n Ca analysis indicated that an apparent equilibrium between the slag and the crucible was reached after abut 75 minutes (see Fig. 29). The weight f final slag generally increased by abut 30%. 40% 35% a 30% U c 25% «20% s= 15% 0 S 10% Si02 Ca _ -.. 5% 0% Melt in Time in minutes at 1250 C Fig. 28: Change f Si02 and Ca cntents in the Kivcet slag

69 S 300 «a cs I * Melt in Time in minutes at 1250 C Fig. 29: Increase f slag weight with time - Kivcet Black fume was bserved ver the furnace when the temperature reached abut 1100 C. This fume cntained sme fine slag, which was ejected int the gas phase during heating and melting. After 30 minutes, the black fume was replaced by gray fume, a mixture f zinc and lead xides. Significant amunts f white and yellw pwders were fund n the brick used as a furnace cver. verall analysis (see Table 10) indicated that the pwder cntained abut 28% zinc and 26% lead. The Ge, In, Sb and As cncentratins in the fume fell in a range f 350 t ppm, indicating a ir recvery f these elements t the gas phase. Table 10: Analysis f the fume - Kivcet Zn (%) Pb (%) As (ppm) Sb (ppm) In (ppm) Ge (ppm)

70 62 In an initial run using 500 grams f slag, a leak f mlten slag ccurred and sme liquid material entered the graphite cup. After that run, grund crucible pwder was added t the slag mixture t prevent ptential leakage. Melting a Charge- Mixture Withut Cpper T make a charge-mixture with the cmpsitin shwn in Table 11, 250 grams f Kivcet slag were mixed with 25 grams f crucible pwder. The charge-mixture was heated t 1250 C and held at this temperature fr 90 minutes. The weight f final slag increased t 358 grams (average f tw runs), indicating that crucible disslutin still ccurred. But the crucible stayed intact and n mlten slag entered the graphite cup. This slag weight increase was cnsidered in the calculatin f metal recveries. Table 11: Analysis f the charge-mixture and the final slags Zn Pb Sb As In Ge Cu Fe 2+ Fe 3+ Si0 2 Ca Al (%) (%) (ppm) (ppm) (ppm) (ppm) (ppm) (%) (%) (%) (%) (%) riginal After hlding withut Cu After hlding with Cu After electrrefining In the slag, sme f the metallic lead vaprized directly t the fume. Zinc and lead xides were reduced by carbn t their metals, which als reprted t the fume. During the perid frm melt-in t 90 minutes, the amunt f trivalent irn ins decreased, while that f divalent irn ins increased. Sme Fe203 was reduced t Fe. Pssible reactins were:

71 63 Pb) = Pb(g) Zn + C = Zn(g) + (g) Pb + C = Pb(g) + (g) Zn + (g) = Zn(g) + C0 2 (g) Pb + (g) = Pb(g) + C0 2 (g) Fe (g) - Fe + C0 2 (g) Fe Pb(l) = Fe + Pb Metal recveries in Fig. 30 indicated that chemical equilibrium was reached after 60 minutes. Abut 8.4% f the zinc and 20.5% f the lead (average) were remved at the apparent equilibrium. These recveries were lwer than thse t be expected cmmercially since the activities f the zinc and lead xides have been reduced by the additin f crucible material. After 90 minutes, zinc and lead cntents in the slag decreased frm 14.0% and 8.4% t 9.9% and 5.3% respectively (see Table 11). Abut 3.0 grams f zinc and 4.0 grams f lead reprted t the fume. The ttal weight lss f the tw metals was very clsed t'the verall weight lss f 10.2 grams. The difference was likely the weight f fine slag ejected during melting. The ttal in equivalents in the slag were calculated using the analysis received frm IPL and assuming that all f the metals f interest in the slag were in the inic state. When the charge was heated frm rm temperature t 1250 C, the ttal in equivalents at melt-in, assuming all inic metals, was After melt-in, the ttal in equivalents decreased as shwn in Fig.31. Since in any reactin, the charge balance must be maintained, it is clear that the metallic lead and the carbn in the slag are invlved and are influencing the charge balance calculatin. If it is assumed that half f the riginal lead present is metallic, the weight f

72 64 carbn required t give an equal charge balance is 0.58 grams r 0.23% f the Kivcet slag. a ii > 2 T3 CS JB X5 S CS H 25% 20% 15% 10% Zn recvery Zn recvery Pb recvery 0 Pb recvery & 0 A 9 " 0 * * Melt in Time in minutes at 1250 C Fig. 30: Metal recveries in the hlding runs withut cpper - Charge mix 0.3 TJ G TJ CS a> t= > > c '3.'" <u B»«u TS «*S 0 W3 w CS V3 <U 4) b 41 s Drp f in equivalents in hlding withut Cu Drp f in equivalents in hlding with Cu A Drp f in equivalents in electrrefining Mles f electrns intrduced in electrrefining ~A" -f Time in minutes at 1250 C 1(D Fig. 31: Decrease in in equivalents during different melting perid and mles f electrns intrduced in electrrefining - Charge mix

73 65 Equilibrating With Cpper When 275 grams f the charge-mixture were melted with 150 grams f cpper, the recvered zinc and lead reprted t bth the fume and the cpper buttn. Reactins (1) t (7) were still pssible, as well as the reactins: Pb(l) = Pb(in Cu) Zn + C = Zn(in Cu) + (g) Pb + C = Pb(in Cu) + (g) Zn + (g) = Zn(in Cu) + C0 2 (g) Pb + (g) = Pb(in Cu) + C0 2 (g) Zn + 2Cu = Zn(in Cu) + Cu 2 0 Pb + 2Cu = Pb(in Cu) + Cu 2 0 Fe Cu = 2Fe + Cu 2 0 After abut 75 minutes, slag reductin, shwn in Fig. 32, reached an apparent equilibrium at which abut 10% f the zinc and 23% f the lead were recvered. A slightly higher metal recvery was btained by using a cpper getter. Again, the ttal in equivalents after melt-in decreased in a similar manner t the runs withut cpper (see Fig. 31). After 90 minute f melting, the ttal in equivalents in the final slag was 0.27 lwer than that in the riginal charge. The amunt f carbn calculated t be in the slag, after cnsidering metallic lead, was similar t that in hlding withut cpper.

74 66 25% 20% I 15% es 10% e s 5% 0% Zn recvery Zn recvery Pb recvery 0 Pb recvery TJ 0 ci " 0 ci _0_ * 9, f " Melt in \ ii m 1 Time in minutes at 1250 C Fig. 32: Metal recveries in the hlding runs with cpper - Charge mix The weight f the cpper buttn increased by 1.5 grams (average) with the cmpsitin shwn in Table 12. The lead cncentratin at 1.4%, althugh lwer than the result f FACT calculatin (6%), was abut 4 times higher than that f zinc and 133 times higher than that f irn. The cpper lss t the slag was als lwer than calculated abve, nly abut 1.3 grams cmpared t the FACT calculatin f 6.6 grams. As discussed earlier, the FACT calculatin is sensitive t the amunt f argn gas available t and in equilibrium with the system. In the experimental wrk, althugh the ttal vlume f argn used was measured, the fractin in equilibrium with the system was nt.

75 67 Table 12: Analysis f the cpper buttns - Charge mix Cnditins Pb (%) Zn (ppm) Sb (PPm) As (PPm) In (PPm) Ge (ppm) Fe (ppm) Cu Hlding with cpper <5 105 Remainder Electrrefining <5 742 Remainder Zinc and lead balances shwn in Table 13 indicated that, after 90 minutes, abut 3.8 grams f zinc (9.8%) reprted t the fume, while nly 0.5 grams f zinc (1.3%) entered the cpper buttn. Hwever, the amunt f lead in the fume (3.0 grams) was nly slightly higher than that (2.1 grams) in the cpper buttn. Althugh zinc activity in the cpper melt is very lw at 1250 C, as indicated by the FACT calculatin, bth melting and biling temperatures f zinc are very lw, nly C and 907 C respectively, resulting in much mre zinc in the fume. The melting pint f lead is nly 327 C. Its biling pint, hwever, is 1740 C. In additin, the lead activity at this cncentratin in the cpper melt is als quite lw. The ttal weight f the tw metals in the fume was 6.8 grams, crrespnding t an verall weight lss f 12 grams in the experiments.

76 68 Table 13: Zinc and lead balance in hlding with cpper and electrrefining - Charge mix Hlding with cpper Ttal In the fume In the cpper In the slag Grams % Grams % Grams % Grams % Zinc Balance Lead Balance Electrrefining Ttal In the fume In the cpper In the slag Grams % Grams % Grams % Grams % Zinc Balance Lead Balance Electrrefining with 5 vlts In the electrreductin runs, 275 grams f the charge-mixture and 150 grams f cpper were melted and subjected t a vltage f 5 vlts fr 90 minutes. Similar t the electrreductin f fumer slags, the vltage increased slightly during the whle electrrefining perid, while the current increased a little in the first five minutes and then decreased slwly (see Fig. 33).

77 Time in minutes at 1250 C Fig. 33: Typical ptential and current in electrrefining - Charge mix In electrrefining, all f the reactins nted abve might ccur, as well as the half-cell reactins: Cathde Zn ++ (in slag) + 2 e " = Zn(in Cu) Pb ++ (in slag) + 2 e " = Pb(in Cu) Ande C (graphite rd) = (g) + 2 e

78 70 and the electrnic cnductin reactins: Fe + e" = Fe Fe " - e" = Fe Zinc and lead were still being remved frm the slag after 90minutes. Abut 3.4 grams f zinc had reprted t the fume. This was nearly 3 times that (1.2 grams) in the cpper buttn. Hwever, the amunt f lead in the fume at 3.0 grams was nly abut ne third f that (8.9 grams) in the cpper (see Table 13). The ttal weight f the zinc and lead in the fume was 6.4 grams, with an verall weight lss f 12.1 grams. Metal recveries were cmpared with thse in equilibrating with cpper (see Fig. 34). The vltage applied clearly enhanced lead recvery. Hwever, the effect n zinc recvery was nt significant. PN 55% 50% 45% * 40% «c 35% N 30% > 25% 1 20% 15% 10% 5% 0% Zn: Electrrefining Zn: Electrrefining Zn: Hlding with Cu Zn: Hlding with Cu Pb: Electrrefining A Pb: Electrrefining Pb: Hlding with Cu A Pb. Hlding with Cu X A. A &. *... 1 s 1 * t 0 \ * * Melt in Time in minutes at 1250 C i Fig. 34: Cmparisn f metal recveries in electrrefining and equilibrating with cpper - Charge mix

79 71 The weight f the cpper buttn increased t grams (average) with the cmpsitin shwn in Table 12. Cncentratins f lead, zinc, irn and the trace elements were much higher than thse with n current applied, indicating a significant effect f the current. The cpper lss was als quite lw, nly 2.1 grams. As shwn in Fig. 31, the mles f electrns per minute intrduced decreased cntinually ver the 90 minute perid, althugh the vltage increased a little. Because f the metallic lead and carbn in the slag mentined abve, the decrease in the ttal in equivalents frm melt-in t 60 minutes was larger than the mles f electrns supplied. After 90 minutes, the ttal in equivalents f the recvered Pb, Zn, Fe, As and Sb in the cpper buttn, after being adjusted by that f the cpper lss, was 0.12, very clsed t the ttal amunt f the electrns intrduced (0.13 mles). If the Kivcet slag was equilibrated with cpper at 1250 C fr 90 minutes and then 5 vlts was applied, zinc and lead cntinued t be remved frm the slag. There was, hwever, n sharp change in metal recvery at the time when the vltage was applied. Fig. 35 shws the zinc and lead recveries in this case.

80 72 Xi CM -a e 90% i 80% 70% + 60% 50% 40% 30% J- - 20% Zn recvery Zn recvery Pb recvery Pb recvery 3 a K- '"9 4J vlts applied - 10% + 0% Mehinl Time in minutes at 1250 C Fig. 35: Reductin f Kivcet slag in the electrrefming runs in which 5 vlts was applied after 90 minutes Repeat Treatment f Kivcet Slag Kivcet slag was treated t remve sme f the zinc and the lead. The slag prduced cntained 9.8% zinc and 2.3% lead. The slag basicity at 0.23 was similar t that f the final slags in Kivcet slag melting. After the treatment, there shuld be n metallic lead and carbn present in the slag prduced. This prduced slag was electr-refined with new cpper and 5 vlts three times (90 minutes each time). The increase in slag weight frm crucible ersin was less than 5% in each run

81 73 and the effect f the newly disslved crucible in each run was very small. After three treatments, althugh zinc and lead cncentratins drpped t 5.9% and 0.3% respectively, metal recveries in the third treatment were still high at abut 20% f the zinc and 50% f the lead present after the secnd run (Fig. 36). Mst f the lead in the slag was remved but the zinc cntent was still quite high. Further refining wuld still be required t recver the remaining zinc. As shwn in Fig. 37, the decrease in ttal in equivalents was rughly equal t the mles f electrns supplied with sme errr particularly in the first sample taken. Ttal in equivalents f the recvered metals (Zn, Pb and Fe) in the cpper buttns in the first, secnd and third run were 0.22, 0.16 and 0.08 respectively, crrespnding t 0.20, 0.17 and 0.12 mles f electrns supplied in the three runs respectively.

82 Zn Recvery (Electrrefining 3 times) > 1 30% 25% 20% = 10% _ m First run Secnd run Third run... * t A A t 0%, k * A Melt in Time in minutes at 1250 C 90 Pb Recvery (Electrrefining 3 times) 60% 50% 40% 1 30% I 20% 10% 0% l ft. First run Secnd run Third run t r * Melt in *. i A * A Time in minutes at 1250 C Fig. 36: Metal recveries frm the slag during electrrefining 3 times

83 75 4-* ra = 1 8" 3 = S 2 2 c ** - 0) i g T3 Q Decrease in in equivalents: First run Decrease in in equivalents: Secnd run Decrease in in equivalents: Third run Electrns supplied: First run Electrns supplied: Secnd run A Electrns supplied: Third run 15" 3TJ "45 T5 "90 1(b5 Time in minutes at 1250 C Fig. 37: Drp f in equivalents and electrns (mles) supplied during electrrefining 3 times

84 ELECTRICAL RESISTANCE MEASUREMENT Slag Measurement At 1250 C, tw graphite rds were immersed int the liquid slag. The distance between the graphite rds was 2 cm r 4 cm. When a vltage was applied acrss the graphite rds, we can write fllwing equatins: Rttai -slag (2cm) = Rslag (2cm) + 2(R cnta ct-l + Rgraphilc + Rcunlacl- 2 ) (>) Rttal-slag (4cm) Rslag (4cm) 2(Ri; 0n tact-l Rgraphite Rcntact-2) Rslag (4cm) _ Rslag (2cm) Rttal-slag (4cm) " Rttal-slag (2cm) (iii) where: Rt ta i -slag (2cm) - the ttal resistance when the distance between the graphite electrdes was 2 cm Rttai-slag (4cm) - the ttal resistance when the distance between the graphite electrdes was 4 cm Rsiag (2cm) - the slag resistance when the distance between the electrdes was 2 cm Rsia g (4cm) - the slag resistance when the distance between the electrdes was 4 cm Rgraphite - the resistance f a graphite electrde Rcntact-i - the cntact resistance between a graphite electrde and a wire frm the pwer supply Rcntact-2- the cntact resistance between a graphite electrde and the liquid slag The ttal resistances, R t tai-sia g (2cm) and Rttai-sia g (4cm), can be calculated using the vltage and the current readings. The results, shwn in Fig.38, Fig.39 and Fig.40 indicated that, when the

85 77 distance between the electrdes was increased frm 2 cm t 4 cm, the ttal resistance increased by nly hm (average) fr the high residual fumer slag, hm fr the lw residual fumer slag, and hm fr the Kivcet slag. In a measurement fr the lw residual fumer slag, the ttal resistance decreased with increasing the distance between the electrdes (see Fig.39). This grup f data was nt used in the abve calculatin. The increase in the ttal resistance was assumed t be equal t R s i ag (2cm)- When the distance between the electrdes was 2 cm, the rati f the distance t the sectin area was similar t that f the slag zne in electrrefining. Therefre, Rsiag (2cm) was als assumed t be the slag resistance in electrreductin Distance between the tw graphite rds (cm) Fig.38: Ttal electrical resistance in slag measurement - High residual fumer slag

86 78 E 8 c i 0.39 i First measurement Secnd measurement Third measurement 1 Distance between the tw graphite rds (cm) Fig.39: Ttal electrical resistance in slag measurement - Lw residual fumer slag E sz First measurement Secnd measurement A Third measurement 1 Distance between the tw graphite rds (cm) Fig.40: Ttal electrical resistance in slag measurement - Kivcet slag

87 79 Accrding t Equatin (i), we have. Rcntact-l + Rgraphite + Rcntact-2 = ^(Rttal -slag (2cm) " Rslag(2cm)) (iv) The left side f Equatin (iv) was named ande resistance (R an de) in electrrefining. The calculatin result indicated that Rande was hm (average). This result can be cnfirmed by a measurement. When the tw electrdes were lifted ut f the liquid slag and their tips cntacted each ther with the vltage applying, the ttal resistance f the circuit was hm. In ther wrds, the fllwing equatin is true: Rcntact-l + Rgraphite + Vl Rcntact-3 = hm (v) where: Rcntact-3 - cntact resistance between the tw electrdes The result in Equatin (v) is a little smaller than that calculated using Equatin (iv). A pssible reasn is that the value f '/2Rcntact-3 is smaller than that f Rcntact-2. Cpper Measurement In the cpper measurement using tw mlybdenum electrdes, we can write the fllwing equatin: Rttal -Cu(2cm) = Rcu(2cm) + 2(Rc 0n t a ct-4 + R]VI + Rcntact-5). (vi) Rttal -Cu (4cm) = Rcu (4cm) + 2(R cnta ct-4 + Rfvl + Rcntact-5) (Vll)

88 80 Rcu (4cm) " Rcu (2cm) _ Rttal -Cu (4cm) " Rttal -Cu (2cm) (viii) where: R t tai -cu(2cm)- the ttal resistance when the distance between the mlybdenum electrdes was 2 cm Rttai -cu (4cm) - the ttal resistance when the distance between the mlybdenum electrdes was 4 cm Rcu(2cm) - the cpper resistance when the distance between the mlybdenum electrdes was 2 cm Rcu(4cm> - the cpper resistance when the distance between the mlybdenum electrdes was 4 cm RM - the resistance f a M electrde Rcntact-4- the cntact resistance between a mlybdenum electrde and a wire frm the pwer supply Rcntact-5 - the cntact resistance between a M electrde and the liquid cpper Again, the ttal resistances were calculated using the vltage and the current readings. The results shwn in Fig.41 indicated that, when the distance between the M electrdes was increased frm 2 cm t 4 cm, the ttal resistance increased by 0 hm in ne measurement and hm in anther measurement. The resistivity f cpper at 1250 C (abut 24x10" hmm) 33 and the rati f the distance t the sectin area in case f "2 cm cpper zne" (abut 25 8 m" 1 ) suggest that Rc u (2cm) is apprximately 6 x 10" 6 hm. Using Equatin (vi), we have Rcntact-4 + RM + Rcntact-5 _ '^(Rttal -Cu (2cm) " Rcu (2cm)) (IX)

89 81 The left side f Equatin (ix) was called cathde resistance (Rcathde) in electrrefining. The calculatin result indicates that Rcathde is abut hm c q H First measurement A Secnd measurement Distance between the tw M electrdes (cm) Fig.41: Ttal electrical resistance in cpper measurement Electrrefining Measurement In electrrefining, we can write Rttai -eletr ~ Rande Rslag(eletr) Rinterce Rcu(electr) Rcathde where: R t tai -eletr - the ttal resistance in electrrefining Rsiag(eietr) - the slag resistance in electrrefining

90 82 R-interce - the resistance f the slag-cpper interce Rcu(eiectr) - the cpper resistance in electrrefining The ttal resistance, R t tai -eietr, can be calculated using the vltage and the current readings. Rande and Rcathde have been defined in the slag and cpper measurements. R s ia g (eietr) is equal t Rsia g (2cm) as mentined abve. In electrrefining, the rati f the distance t the sectin area in the cpper zne is abut 10 m" 1 and the cpper resistance, Rcu(eiectr), is almst zer. Having the abve data, we can calculate the resistance f the slag-cpper interce and determine vltage distributin in electrrefining. The results shwn in Table 14 indicated that the resistances f the slags in electrrefining were very lw. Mst f the ttal vltage fcused n the ande (abut 15%), the slag-cpper interce (40-50%) and the cathde (30-40%).

91 Table 14: Vltage distributin in electrrefining High Residual Fumer Slag Item Resistance Vltage hm % Vlts % Ttal Ande Slag Slag-cpper interce Cpper Cathde Lw Residual Fumer Slag Item Resistance Vltage hm % Vlts % Ttal Ande Slag Slag-cpper interce Cpper Cathde Kivcet Slag Item Resistance Vltage hm % Vlts % Ttal Ande Slag Slag-cpper interce Cpper Cathde

92 84 8. NUSINS Metal recvery frm MIN's fumer slags and Kivcet slag under different cnditins was tested in this study. Vltage distributin in electrrefining was als rughly defined. The fllwing cnclusins have been drawn. Metal Recvery frm the Fumer Slags Even heating withut cpper, sme zinc, lead and trace elements indium and germanium culd be remved frm the fumer slags. The main cntents in the fume were zinc and lead xides. Sme trace elements (In, Ge) were als fund. When cpper was used as a "getter", a higher lead recvery was btained frm high residual fumer slag. Hwever, zinc recvery frm bth fumer slags was nt imprved. Sme zinc and lead were recvered frm the slags t the cpper melt. In electrrefining, zinc and lead recveries frm high residual fumer slag were enhanced by the vltage applied. But the effect f current n metal recvery frm lw residual fumer slag was nt nticeable. Abut 50% f the zinc and mst f the lead were remved frm the fumer slags by 90 minute f electrreductin. The zinc in the fumer slag culd nt be remved when its cntent was lwer than abut 0.5wt%. Metal Recvery frm the Kivcet Slag FACT calculatin indicated that the Kivcet slag has a significant self-reductin

93 85 ptential. Metal recvery frm the Kivcet slag will be influenced dramatically by the disslutin f the fireclay crucible. Simple hlding f the charge-mixture (Kivcet slag was mixed with the crucible pwder at a crucible/slag weight rati f 1/10) at 1250 C permits sme zinc, lead and trace elements such as Sb, As, In, Ge t be recvered. The main cntent f the fume was zinc and lead xides. When cpper was used as a "getter", zinc and lead recveries were a little higher than thse in hlding withut cpper. Abut half f the recvered lead entered the cpper, while mst f the reduced zinc vaprized t fume. Lead recvery using electrrefining was imprved ver equilibratin with cpper. Hwever, zinc recvery was nt nticeable enhanced. Kivcet slag was treated t remve sme f the zinc and the lead and then was electrrefined 3 times. Mst f the lead was recvered. Hwever, zinc cncentratin was still as high as 6%. Further treatment wuld be required. The experimental results were biased by the disslutin f the acidic crucible. Kivcet slag is very crrsive. A significant amunt f the fireclay crucible disslved int the slag at high temperature. Slag weight generally increased by 30%. Recveries in an industrial system, where the activities f the principal metal xides wuld be higher, wuld be expected t be better than thse reprted.

94 86 Vltage Distributin in Electrrefining The resistances f the slags in electrrefining were very lw. Mst f the ttal vltage fcused n the ande (abut 15%), the slag-cpper interce (40-50%) and the cathde (30-40%).

95 87 R E F E R E N C E S 1 S. W. K Mrgan, Zinc and Its Allys and Cmpunds. Ellis Hrwd Limited, 1985, p Fengxiang He, "A NVEL METHD FR METAL REVERY FRM ZINC FUMING SLAGS", M.A.Sc. Thesis, Rbert lsn, "Summary f Summer 2001 Kivcet Slag Treatment Wrk" 4 A. R. Babcck, R. A. Franc, A. C. Mikrvas, S. Bharmal and M. I. Cecchini, "PREPARATIN AND START-UP F MIN'S NEW LEAD SMELTER", Zinc and Lead Prcessing. 1998, pp D. W. Ashman, "PILT PLANT AND MMERCIAL SCALE TEST WRK N THE KIVCET PRCESS FR MIN'S NEW LEAD SMELTER", Zinc and Lead Prcessing. 1998, pp Data f THE METALLURGICAL SCIETY, http ://www. metsc. rg/virtualtur/prcesses/zinc-lead/kivcet. asp 7 G. G. Richards, Teck-Cminc Research, private cmmunicatin, FACT is a thermdynamic sftware prgram that slves equilibrium prblems by a Gibbs Free Energy minimizatin technique. It is available thrugh the CRCT (Centre fr Research in Cmputatinal Thermchemistry, Ecle Plytechnique (Universite de Mntreal), Bx 6079, Statin Dwntwn, Mntreal, Quebec, CANADA H3C 3A7 9 L. V. Slbdkin and G. F. Kluev, "KIVCET PRCESS - A UNIVERSAL TECHNLGY FR TREATING LEAD NTAINING MATERIALS", Zinc and Lead Prcessing. 1998, pp

96 88 10 S. L. Brwn and A. B. Neil, "ASAR'S GLVER LEAD PLANT", Zinc and Lead Prcessing. 1998, pp S. W. K. Mrgan and S. E. Wds, "THE PRDUCTIN F ZINC IN A BLAST FURNACE", Zinc-The Science and Technlgy f the Metal. Its Allys and Cmpunds. American Chemical Sciety Mngraph Series, N. 142, 1959, pp A. Siegmund, R. Puellenberg and A. Rhkhl, "QSL-STLBERG, GERMANY - LEAD SMELTING IN THE NEW MILLENNIUM", Zinc and Lead Prcessing. 1998, pp G. Curtney, Prc. Australas., I.M.M., N.S., n. 38, 1920, pp R. B. Caples, J. Amer. Zinc Inst, vl.14, 1931, pp G. E. Murray, Trans. Canadian I.M.M., vl. 36, 1933, pp G. G. Richards, J. K. Brimacmbe and G. W. Tp, "KINETICS F THE ZINC SLAG- FUMING PRCESS: PART I. INDUSTRIAL MEASUREMENTS", Metallurgical Transactins B, 1985, vl. 16B, pp G. G. Richards and J. K. Brimacmbe, "KINETICS F THE ZINC SLAG-FUMING PRCESS: PART II. MATHEMATICAL MDEL", Metallurgical Transactins B, 1985, vl. 16B, pp G. G. Richards and J. K. Brimacmbe, "KINETICS F THE ZINC SLAG-FUMING PRCESS: PART III. MDEL PREDICTINS AND ANALYSIS F PRCESS KINETICS", Metallurgical Transactins B, 1985, vl. 16B, pp G. Assis, "EMERGING PYRMETALLURGICAL PRCESSES FR ZINC AND LEAD REVERY FRM ZINC-BEARTNG WASTE MATERIALS", Zinc and Lead Prcessing. 1998, pp

97 89 20 Masud A. Abdel-latif, "FUNDAMENTALS F ZINC REVERY FRM METALLURGICAL WASTES IN THE ENVIRPLAS PRCESS", Minerals Engineering Internatinal nline, 21 C. Mattich, K. Hasselwander, H. Lmmert and A. N. Beyzavi, "ELECTRLYTIC ZINC MANUFACTURE WITH WAELZ TREATMENT F NEUTRAL LEACH RESIDUES", Zinc and Lead Prcessing, 1998, pp Supachai Surapunt, Y. Takeda, and K. Itagaki, "DISSLUTIN F ZINC IN Ca0-Si0 2 - Fe SLAG EXISTING WITH LIQUID Cu-Zn-Fe" Jurnal f the Mining and Materials Prcessing Institute f Japan, vl. Ill, issue: 8, July 1995, pp K. Azuma, S. Gt, and. gawa, "THERMDYNAMIC STUDIES N ZINC XIDE IN SLAG", J. Fac. Eng. Univ. Tky, Ser. A, 5, 1967, pp A. W. Richards and D. F. J. Thme, "THE ACTIVITIES F ZINC XIDE AND FERRUS XIDE IN LIQUID SILICATE SLAGS", Physical Chemistry f Prcess Metallurgy. Part I (Ed. G. R. St. Pierre), 1961, pp S. Wright, W. T. Denhlm and W. J. Rankin, "THE ACTIVITIES F ZINC AND LEAD XIDES IN LEAD BLAST FURNACE SLAGS", Nn-Ferrus Smelting Sympsium, September 1989, Prt Pirie, SA: 100 years f lead smelting and refining in Prt Pirie, AusIMM/I E Aust Prt Pirie Cmbined Grup. Series: Sympsia series (Australasian Institute f Mining and Metallurgy); 6/89, pp Yichi Takeda, "ACTIVITIES F LEAD AND ZINC XIDES IN Ca-Si0 2 -Fe SLAG", Zinc & Lead '95. Prceedings f the Internatinal Sympsium n the Extractin and Applicatins f Zinc and Lead, Sendai, Japan, May 22-24, 1995, edited by T. Azakami... [etal.], pp

98 90 Supachai Surapunt, Rdriguez R. Vazquez and K. Itagaki, "ACTIVITY MEASUREMENTS IN LIQUID Cu-Zn-X (X = LEAD, SILVER, GLD) TERNARY ALLYS", Jurnal f the Mining and Materials Prcessing Institute f Japan, vl. 110, issue: 8, July 1994, pp Supachai Surapunt and M. Hir, "ACTIVITY F ZINC IN MLTEN Cu-Zn-Fe TERNARY SYSTEM", Jurnal f the Mining and Materials Prcessing Institute f Japan, vl. Ill, issue: 8, June 1995, pp F. D. Richardsn, Physical Chemistry f Melts in Metallurgy. Academic Press, Lndn and New Yrk, 1974, vl. 1, p60 30 Carls Diaz, "THE THERMDYNAMIC PRPERTIES F PPER-SLAG SYSTEM". Incra Series n the Metallurgy f Cpper, 1974, p68 31 Walter R. Dicksn and Edward B. Dismukes, "THE ELECTRLYSIS F Fe-Ca-Si0 2 MELTS", Transactins f the Metallurgical Sciety f AIME, 1962, vl.224, pp Junius David Edwards, Francis C. Frary and Zay Jeffries, Aluminum and Its Prductin. Chemical Engineering Series, McGraw-Hill Bk Cmpany, Inc., New Yrk and Lndn. 1930, pp G. T. Dys and T. Farrell, Electrical Resistivity Handbk. Lndn, U.K.: Peter Peregrinus n behalf f the Institutin f Electrical Engineers, 1992, p. 206

99 APPENDIX-1: ANALYSIS F THE SLAG SAMPLES AND THE CRUCIBLE 91

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