The 1976 Extractive Metallurgy Lecture The Metallurgical Society of AIME I Direct Leaching of Sulfides: Chemistry and-Applications ERNEST PETERS ‘The sulfide minerals associated with copper, nickel, zine, lead, and molybdenum concen- trates are described according to their thermodynamic stability zones on Eh-pHt dia grams. From th zones, the chemistry assoeiated with various thermodynamically feasible decomposition paths is diseussed, and process developments associated with the ‘most favorable decomposition paths are briefly reviewed, Extractive metallurgy consists of the science and art of obtaining commercial grades of metal from ore material mined from the earth's erust. For reasons of marketability, the final metals are almost always standardized products; on the other hand, the ores from which extraction starts are enormously diverse. How does a metallurgist devise a process and design 2 plant around a newly discovered ore body (or, for that matter, a new plant for an old ore body) that will produce standard metal products in such a way as to justify the investment ? ‘The most customary answer to this question is to concentrate the ore by means of a standard mineral dressing operation, and then to smelt the eoncen- trates, again, in a relatively standard way. A refin- {ing process completes the route to marketable grades of metal. This answer works particularly well for those metals found in nature as sulfide minerals, be- cause a) they are relatively easy to concentrate, and b) the sulfur supplies part of the fuel energy re- quired in the smelting operation. Furthermore, at ‘smelting temperatures, the ore minerals lose their The Burin Metal Latare war uaz 1959 to provi on ound ‘gman nthe i of nonfrous metal ar carer a the onl AME ERNEST PETERS has had distin crerin oth education snd in industry, His andamental end pats workin coper nd me! hy demetalNey tas been of pioneering importance tthe leon and to the mites ins, ‘He has been an act, constructive member ofthe AIME with contbton to both The MetatnglSoity andthe Sait of Mining Engine Peter received A Se MA Se, and PAD deer at ihe Univer of METALLURGICAL TRANSACTIONS 8 ‘dentity in a molten mass, and the technical and Scientific problems are limited to choosing operating conditions dictated by thermodynamfes, mass transfer Kinetics, and phase separations. There is now an ex- cellent body of scientific knowledge and engineering experience in these areas, and so this processing problem responds with good reliability and predicta- bility to a rather mature science and technology. However, two new problems have confronted us in this last quarter of the twentieth century, related to the exponentially increasing density of human settle- ments on a finite planet. These are environmental pollution and energy shortages. The metal extraction industry has become an early vietim of the public concern for these problems; the tall stack is a highly visible source of air pollution, and the hunger for energy by the metal extraction industry appears to be well known. Environmental restrictions may make it ‘uneconomic to use sulfur for fuel, and the metallurgist must consider the conflicting rumours that hydrometal- lurgy offers pollution-free processes, or that it con- sumes excessive quantities of energy. What does hy- ‘it Columbia allowing ser a the Royal Canain AlcFe. Air nd tla expeenes with U.S Sel Corp. Cominco, id and Usa Cable Corp he retured tothe Unive of Bish Catan 1958, and advanced tht een poaion of Poet in 1968, "is conn ems hav cided Cominco Ls, Tex Canada, Li, ‘ran Mining Ca, Kenecot Copper CoE. -DuPomt de Nemout Co, and Pacer Developmen, Li een eed the Exact MetuyDivion Best Paper Awad ie VOLUME 78, DECEMBER 1976-sosdrometallurgy have to offer in terms of performance and economics for a new kind of plant? Must we an- ‘wer in terms of state-of-art, or are we permitted to be truly innovative, hoping for a break-through with an untested technology? Hydrometallurgy does not offer a generalized, brute-force solution to the recovery of nonferrous ‘metals from sulfide minerals. The mineral chemis- try of direct leaching is highly individualistic. The mineral decomposition rates vary greatly, even for the same mineral from different mineral assemblages. ‘The chemical agents used to decompose minerals hydrometallurgically vary substantially in their reac- tivity and in their inorganic chemistry. However, hydrometallurgy has a few things going for it: at low temperatures, mixing entropies are small, so small thermodynamic differences between ‘metals can lead to large separation factors; there are a few important leaching reactions that are fast ‘enough to be diffusion controlled, even at room tem- perature; and unreactive gangue minerals can usually pass through leaching processes without significant ‘energy consumption. If a satisfactory hydrometallurgi- eal process can be devised for a certain type of con- centrate, there should be more latitude at the mill for lowering concentrate grade (if better recoveries result) than for a comparable smelting process. These special possibilities of hydrometallurgy suggest that {ideally the resulting plants should not only replace conventional smelters, but also eliminate refineries (by producing marketable metals directly) and lower the cost (as well as increase recoveries) at concen trators. ‘The following represents a selection of nonferrous sulfide minerals and concentrates historically treated by pyrometallurgical means, that seem to be Important candidates for a new hydrometallurgical technology. Some of these have, of course, appeared in the techn!~ ‘cal and patent literature, and a number of technically successful pilot plants, and even a few commercial plants already exist. ‘THE SULFIDE MINERALS Five nonferrous metals account for almost all of the sulfur emissions from smelters (including roasters) today, and their relative significance is shown in Table 1. Some of this sulfur is recovered, bat the larger part continues to be emitted as atmo: pheric $0; through tall stacks. ‘Most of the significant minerals contained in non- ferrous sulfide concentrates of these metals are listed in Table II. Any decomposition chemistry com mitted to direct leaching must contend with the in- “Tae. Sar Content of Nonferrous Conc” (0974: Hilon of Short Toms) Concent Fre World USA ona Gopper 60 1s 09 Nott 20 e ts ‘ie as os os tess 08 ais 008 Mlybdemon 08 0% oot "Este from E & MJ Sunol Daa on Metal Podocton, Mc, 1978, 506-VOLUME 7B, DECEMBER 1976 Table, Sule Miura of Sgntomes in Nonfarous Conant pper Concent sa 20 Opera Cues; Covetite cus 181035 pote Case, Chalease Cos 25035 FeS | DigeieCaua8 Minor and peciou metals casts, BAS” bt Nickel Concentrates Gt Spot Mires. No2pet co Tyetote Pega oper Ghaleopyite—CaFeSp apts Cabanite—CuFeSy Mio ed precious metals ie Concentrate $5 1060 pet Za Splaeste a8 05 t02pe1Po Mammaite (Zn, Fo)S 2 12paFe Gaent Ps Oto 2percu Pyne Fess Minor and prcous met Pyrite Fava ies Ps Spheste ZS 210 25pctFe Pyate RS, ote2 pec Pynhotte Fes. Minor and precious meal Sher mins Molyidena Conner Ss etme Mlybiente Mos, 37 pets rate PS, 30 Fe, Cu, Re dividual decomposition chemistries of these minerals. ‘The hydrometallurgist must understand both the ther- modynamies and the Kinetics of decomposition paths for these minerals before he can devise the best ‘Separation steps between nonferrous metals, iron, sulfur, and gangue minerals. There is a real short. age of knowledge on the decomposition chemistries of these minerals, and this continues to restrict the development of truly competitive hydrometallurgical processes for these five principle metals. Where hard laboratory studies have unravelled some of this chemistry, useful processes have resulted, as in the case of the Sherritt Gordon Mines Ltd. process for nickel,' the Anaconda-Arbiter processes for copper and the Falconbridge matte leach process for nickel ‘THERMODYNAMICS OF SULFIDE MINERALS ‘The stability (or instability) of sulfide minerals in contact with aqueous solutions of selected composition can be summarized by means of Eh-pH diagrams.* Sich igre ar afl tyrone allt ae Eling gra 0 prrometlgte ‘The diagram of interest to copper hydrometallurgists 4s approximated” in Fig. 1, and defines regions of pi “Tis diagram incomes ad accurate Besse neglects he xine of the mineral nt (Co), evhanite Cafe), Hate (CFS and ao be. case the proper of protest ted to tee of chanel eS. ‘and potential in which the copper minerals chalcoct covellite, bornite, and chalcopyrite are stable, to- gether with pyrrhotite, pyrite, and elemental sulfur. Such a diagram permits identification of those prop- erties of an aqueous solution in which a mineral is in- stable and should decompose, and it also identifies any new solid or gaseous phase that should form dur- ~ ing such decomposition. Tt does not indicate the rrate of decomposition of an unstable mineral; this ‘can vary from rates go fast that they are controlled METALLURGICAL TRANSACTIONS 8= vour isner Fig. 1-Eh-pH dlagram of the Cu-Fe-S-Hh0 system at 25°C: all solutes at 0.1 M activity except Cus* = 0.01 M. All reac {ons reversible, by mass transfer limitations, to rates so slow that geologic time periods are required for the evidence to be directly observed. Four different kinds of solutions in which a sulfide mineral might decompose can be identified in Fig. 1. 1) Oxidizing solutions, leading to a) elemental sulfur or b) sulfate ions in solution, depending on the oxidiz~ ing potential and the selected pit. 2) Strong acid solutions, leading to H,S evolution and dissolved expper and/or iron 3) Reducing solutions, leading to H.S evolution or sulfide ion formation and lower valence sulfide or ‘metal phase. In Fig. 1 there is an acid reduction re- gion where chalcopyrite would yield Fe++ in solution and Cus$ or Cu as solids, but at lower potentials both Fe and Cu would tend to form. 4) alkali solutions, leading to sulfide ions in soution mai etal der fr lowes slides) ‘The above four systems are generally applicable to all metal sulfides, although the strong acid limits 2) or strong alkali limits 4) are sometimes beyond the strengths available for real aqueous systems. The oxi- izing 1) and reducing 3) systems can be further sub- divided into acid systems and allali systems. Oxidation of the mineral chalcopyrite at successively higher potentials in the acid region (pH{ = 0) of Fig. 1 can be expressed by the following stoichiometric equa- tions: CuFeS: + 0.4148 + 0.80x* ~ CuF en:S04 + 0.8 FeSs bornite pyrite +088" +0.80x [1] CuFeS: + 0.515 + Ox CuSys + FeSs +H" + Ox chaleocite [2] CuFes: +S +20x—~ Cus . + FeS, + 2H" + 20x" covellite Is) METALLURGICAL TRANSACTIONS 8 CuFeS. + 20x — CuS + Fe + i + 20x" [a] CuFeS,; + Cut+ > 2CuS + Fe" (4a) CuFeS, + 6H,0 + 90x— CuSys + Fe + 1.580; +128" +905" [5] CuFeS, + 8H.0 + 160x— Cu? + Fe + 2803 + 16H" + 160x". [8] identified except in (4a). gs. [1] to [8] applicable to the bornite, chalcocite, and lower covellite stable regions, require HS as a reactant, while pyrite Fes; is a produet. If HS Is not supplied as a reactant, either by the experimenter or by a side reaction on the minerals present, these reactions will not take place. Even if H:8 is available, ro decomposition of chalcopyrite can oceur in these regions of pif and potential unless pyrite can nucleate and grow. None of these reactions have been reported under laboratory time periods, and they are unlikely to occur. Reaction [4] 1s a covellite forming reaction expected in the elemental sulfur~stable region of Fig. 1. It has ‘been observed by Dr. David Jones* in our labora~ tories when chalcopyrite is oxidized by anodization above about 180°C in a pressurized system. Reaction [4a] was observed and patented for hydrometallargical purposes by McGauley” in a hydrothermal system ‘perating inthe 160 to 280°C range. However, covel- lite has not been observed as an observation product of Chaleopyrite in any atmospheric or pressure leaching studies.* “Or cone cv rid) and pie nb ome rom oye and salaries inl teal tenet 47 RE) Reaction (5] produces chalcocite by oxidizing chal- copyrite at low potentials; the reaction is too slow to observe under laboratory conditions, but is important geologically, where it accounts for the presence of haleocite in oxidized copper ores. Tt may also be an {important reaction in dumps, where bacterial action ac- celerates the chemically slow sulfur oxidation. Eq. [6] is a regularly observed reaction in labora tory leaching tests, especially at high pH, as in am- ‘monia leaching. In acid oxidizing leaches it accounts for sulfur oxidation ranging from less than 1 pet to more than 30 pet depending on the pHi and the oxidant. None of the Eqs. [1) to (6) interpreted from the Eh DH diagram (Fig. 1) account for the dominant reaction observed in acid oxidizing leaching, as described by Eq. [7]: CuFeS, +40x-- Gu + Fe" +28+40x. [7] Im fact, Cuts is an oxidizing agent capable of oxidizing sulfur, and 50 this observed reaction is found ex- clusively because a) sulfur is oxidized to sulfate with {great difficulty (at least in acid solutions) by a very Irreversible path, and b) the rate of Reaction (7] is very favorable, by comparison to any of the first six ‘equations. ‘When lines on the Eh-pHf diagram (Fig. 1) represent ing unobserved reactions (in the laboratory, not geolo- VOLUME 7B, DECEMBER 1976-507=e oes gical sensé) are deleted, it is possible to obtain » new diagram of more value to hydrometallurgists: Fig. 2 shows the extension of the ehaleopyrite-stablo* zone “Aetna ‘SBtained when Reactions [1] to [3] are eliminated (i.e. 4 is not available as a reactant and/or pyrite can not form at a measurable rate). This diagram still ‘contains some reactions observed only at very ele- vated temperatures (Eq. [4)) and in geological times {Gq. (5) which could be eliminated in a further evolu tion of useful diagrams for hydrometallurgists. ‘Since leaching commonly takes place in aqueous systems containing specific reagents that lead to new compounds oF complex fons in solution, itis worth while to incorporate these reagents into the Eh-pHl diagram where the thermodynamic effects can be re- vealed. In the copper-iron-sulfur diagram, chloride {ons (at 1 M) are incorporated in Fig. 3 and ammonia (or ammonium ons) are incorporated in Fig. 4. Its clear from these two diagrams that neither reagent ‘Significantly alters the stability zones of sulfide phases; almost all ofthe effects are in regions where Copper is in solution, oF present as an oxide. The metallic copper stable zone is penetrated somewhat by ammonia. We can conclude that the main ther- modynamic effect of chloride or ammonia during Teaching is to prevent formation of oxides that would ‘otherwise slow down the reaction between sulfide minerals and the aqueous solutions. Of course, these Teagents may play many other roles in the remainder of a hydrometallurgical circuit. Copper Processes ‘New copper processes involving oxidative leaching have received a great deal of attention in recent years. Inventors and researchers have proposed am- moniacal systems,*"’ acid sulfate systems,* chloride systems,” and nitrate systems."* ‘With apologies to the rest, I will discuss only one direct leaching pro- eas for copper concentrates our own'? shown in Fig. 5~that uses an acid ferric chloride leaching ‘media. This process-has never been piloted, but has received careful study on a bench scale, in rather large lots (50 gal). The evidence is that copper_ex- tractions are unbelievably high (99.95 pet); that pyrite and molybdenite are unattacked; that elemental sulfur 4s obtained in greater than 98 pet yield (from chalco~ vour (she) POTENTIAL. oa Fig. 3—Same as Fig. 1 except chloride fon present at 1 M. activity = vour (she) Pore nriat a a oH Fig. 2Same as Fig. 1 except the following reactions not re~ versible: H,S not consumed: FeS, not formed. 508-VOLUME 78, DECEMBER 1976 vour (sHe) ee a Fig. 4—Same as Fig, 1 except NHly (pit > 9.25) oF NI (pH 4:25) present at IM activity. METALLURGICAL TRANSACTIONS 8COPPER wronoUETALLUNGY Fenmic CmLOMIDE LEACH PROCESS [SSRIs te Cures; +H" _ CuSas_ + 0.5F8" +05 Fes, ~ ehaleocite ~ : ross || } CuFeS.+2H'— Cus. + Fe" + HS fio) covellit (CuFeS, + 4H" > Cu + Fe" + #5). tu Im general, none of these reactions seem to have been observed. The most probable of these reactions 1s Eq. [10] because it does not require the nucleation of pyrite. Eq. [11] expresses a reaction that is not thermodynamially favorable at accessible pH values. ') Reductive decomposition, Fig, 5~Copper hydrometallurgy flow sheet after Milner et I al.it (The UBC-Cominco Process). pyrite); that “pare” iron oxide, suitable for sponge fron manufacture, is separated as a granular, anhy- drous, filterable Solid; and that minor metals and precious metals are completely recoverable from Solutions or residues. Copper is refined chemically as CuCl erystals, permitting the production of metallic ‘copper that is marketable without refining. Careful ‘cost estimates on the flow sheet shown in Fig. 6 indl- cate that costs are competitive with smelting and refining, and that energy demand for this process is intrinsically very low. Of course, since the process has not been engineered, there could easily be hidden problems that prevent the achievement of estimated performance. Cominco, Lid. the assignees and spon- 80r8 of this process, has opted for a pilot plant study of another hydrometallurgical process based on an acid sulfate system. This process, known as the SC process (for Sherritt-Cominco) was developed jointly by the two companies and is undergoing pilot plant trials at Fort Saskatchewan, Alberta this year. The SC process has indicated costs as good as (or better than) the ferric chloride process just described, bat a detailed description of the process is not yet available. As previously suggested, there are other ways of decomposing chalcopyrite besides oxidative leaching. Some nonoxidative decomposition paths indicated by the thermodynamics of Fig. 1 or Fig. 2 include the fol- lowing. a) Acid decomposition I CuFeS, + 0.81" ~ CuFeasSes + 0.4 Fe + 0.4 FeS: bornite + 0.418 {a} METALLURGICAL TRANSACTIONS B CuFeS: + 2.4H" + 0.8R* ~ CuFep:Sas + 0.8 Fe" +i2ns+0.8R' [12] Tim eid cig et CuFeS, + SH" + R— Cufs + Fe" + 15 8+ R” [13] CuFeS, + Ht + Cu” — 2CuSas + Fe + HS {13a} CuFeS; + 4H" + 2R— Cu" + Fe + 2H,S+2R* (14) CuFeS; + 4H" +4R— Cu’ + Fe’ + 2H,S + 4R*. [15] Similar equations could be written for higher pH values that stabilize HS" or S” and FeS instead of H,S and Fe. However, the acid reductions are the most interesting because they suggest that the key separa- tions can all be made: iron can be held in solution, sulfur can be eliminated as H,S gas, and copper re- tained as a solid (Eq. [14]). The reductive decomposi- tion of chalcopyrite hag been observed; in particular, Hiskey and Wadsworth” observed and reported Reac~ tion [19a] and Biegler" has reported Reaction [13] {in an electrochemical cell that exerted a cathodic current on copper concentrates. The latter reaction ‘was somewhat inefficient, with hydrogen evolution oc~ curring at the same time. ©) Alkali decomposition ‘The Eh-pHl diagram (Fig. 1) indicates that chaleo- pyrite is unstable at high pil values, going over to bornite or chaleocite and magnetite. The relevant stoichiometric equations are: Cures: + 2.4087 CuFexsSas + 0.267 FesOs + 1.1678" + 1.21.0 + 0.03380; [6] CuFeS; + 80H” — CusSas + 0.38 FeO, + 1.838* + 1.5H,0 + 0.042803. fan Although neither of these reactions have been de- scribed, Baratin"” has some evidence that magnetite and sulfide ions are formed when chalcopyrite is di gested at 200°C with caustic soda. The reaction rate ‘of Eqs. [16] and [17] can be expected to be very slow. In summary, then, it is evident that only the oxida- tive leaching of copper concentrates, either in acid or ammoniacal systems, has drawn substantial interest from investigators looking for a new copper process. Acid or alkali decomposition of chaleopyrite does not look promising at all, but there may be a useful route for breaking down this most resistant of cop- per minerals in reductive processes that separate iron and some of the sulfur, leaving the very reactive VOLUME 78, DECEMBER 1976-509‘mineral chaleocite (with any noble impurities) in ‘quantitative yield. NICKEL ‘The processing of nickel sulfide concentrates may not be of significance in the U.S.A., but it is of utmost importance in Canada and other parts of the world (see Table 1). As in the case of copper, it is useful to examine the Eh-pH diagram (Fig. 6)* which permits *Uaforaaly, our sts fr rice mines ae not mature as thos For oper mers, andso a apam containing the allinpvtant mineral Pent Tani (NF) Ss ot wale ‘Scrutiny of the alternate Foutes by which nickel sul-— fides can be decomposed. Two processes exist for ‘the direct leaching of nickel sulfides: the oxidizating ammonia Jeach, pioneered by the late Professor F. A. Forward" and practiced today by Sherritt Gordon Mines, Ltd. at Fort Saskatchewan, Alberta, by West ‘ern Mining Corporation at Kwinana (Western Aus tralia), and by Impala Platinum Ltd. at Springs, TVL., South Africa.” The flow sheet for this process is given in Fig. 7. Basically this process oxidizes both metal and sulfur in the mineral, and ammonia provides the ‘complexing agent for holding nickel in solution until it is hydrogen reduced to metal. Because sulfur is oxidized to sulfate, the process is a heavy oxygen consumer and ultimately a producer of ammonium sulfate. The product is a fully marketable, high grade nickel powder, that has earned for itself some lunusual applications because of its form and parity. ‘The process is applicable to both nickel concentrates and nickel matte. ‘More recently, P..G. Thornhill ef al® presented a new hydrometallurgical process developed for Fal- conbridge Nickel Mines, Ltd. that is based on acid decomposition of nickel sulfide, with hydrogen sulfide ovenMA, = wour (ant anges s Fig. 6Eh-pHl diagram for the Ni-Fe-S system at 25°C. Standard conditions. S10-VOLUME7B, DECEMBER 1976 er cova A] etal Poms =I "ec, snes = ——{ ‘San ae Jos mae Arey Fig. 7—The Sherritt Gordon ammonia leach process for nickel sulfide concentrates. as the product. The flow sheet is shown in Fig. 8. This process is successful because hydrochloric acid of high strength (275 —~ 165 g/1) is used and at these con centrations the thermodynamic activity of HCl is known to be very high,” equivalent to a pH range of about —1.6 toi. It is evident from Fig. 6 that in this pH range both NiS and NisS> are completely decom- posed (with generation of HS and H). ‘Examination of the Eh-pHl diagram (Fig. 6) reveals that nickel sulfide decomposition could occur by about four reaction directions. a) Alkali oxidation NiS + 5H,O + 8Ox— NiO +SO7+10H"+ 80x" [18] (with ammonia, NiO + 2NH; + 4NHy — Ni(NH)é' +H,0) i1sa] b) Acid oxidation NIS+ 20x— Ni"* + 8° + 20x° Ls) ©) Acid decomposition Nis + 2H" Ni" +S (20) NiSy + 6H" SNI" + 2118 + Hy (a) 4) Reduction NiS, + 411" + 4R— NI" + 288 + Re. (22 While path a) leads to the suecesaful Sherritt Gordon ammonia leach process and path e) to the successful Falconbridge Matte Leach Process, there is no ev\- dence for a useful application ofthe acid oxidation b) although the chemistry must have been observed. ‘The reduction d) has not heen reported and may be sob- Servable because nickel is a metal with too low a hy- drogen overvoltage to permit Reaction [22] to continue After the first traces of nickel are formed. [METALLURGICAL TRANSACTIONS+ teeaieg seuton ») Acid decomposition ZnS + 2H! ~ Zn" + 1S ©) Reduction ZnS + 2H" + 2R— Zn’ + H,S + 2R+ ZnS + 2R— Zn’ +S" +2R+ 4) Alkali decomposition ZnS + 40H — Zn03 + 8° + 2140. (ar) ‘The oxidizing reaction producing sulfate (Bq. [28b]) 1s present to a minor extent in acid pressure leaching discussed previously, and was utilized by Veltman fand O’Kane” as a separate step to generate make-up (24] (2s) [28] (ies) (a sauion | cists [ie Sion PT Recovery] Fig. 6—The Falconbridge Matte leach process for nickel maize. zinc ‘The Eh-pHf diagram for the Zn-S-H.O system is, shown in Fig. 9. It is rather simpler than the sys~ tems for copper and nickel, in that only one sulfide ‘phase is shown; the mineral sphalerite. An iron ‘containing variety of ZnS, marmatite, makes very Little difference to the thermodynamies. The mineral ean be decomposed in principle by oxidation, acidifi- cation, reduction, or alkali decomposition, as ready discussed for copper and nickel minerals. (Of these routes to zine sulfide decomposition, only oxidation under acid conditions has received much at- tention, The sulfuric acid-oxygen pressure leach was first studied by the late Professor F. A. Forward land eoworkers."* Later, the process was piloted several times, and an economically optimized flow sheet (Fig. 10) was developed by Veltman and O"Kane.* ‘This path to direct leaching of zine concentrates still seems to be the best way to go, because it inter- igrates well with conventional roast-Jeach-electrowin circuits, and recoveries are generally high~especially ‘on iron-containing or marmatitic concentrates com- pared to recoveries from roasted calcines. Further~ more, elemental sulfur is obtained in good yield, and residues are acceptable as lead smelter additions after sulfur is removed. ‘The chemistry of reactions involving the decomposi- tion of zine sulfide is represented by the following equations. 'a) Oxidation ZnS + 20x— Zn" +S* + 20° ZnS + 41,0 + 8Ox—~ Zn" +80} + BHT + BOX” (23a) {230}. METALLURGICAL TRANSACTIONS B your (sne) ns Tr Fig. 9-Eh-pll dlagram for the Z-8-H,0 5 ‘Standard condition TT I Fig 10—The accelerated acid pressure leach process (Sher THE Gordon) for sino after Veltman and O'Kane. VOLUME 7B, DECEMBER 1976-511sulfate to that lost as lead sulfate in residues. The ‘acid decomposition (Eq. [24)) has not been seriously studied because of the low pH associated with high zinc concentrations (pH = 1.5 at 1 M-Zn" from Fig. 8). However, zine sulfide should dissolve under the same conditions as the Falconbridge matte-leach process with 275 ¢/1 hydrogen chloride, and the ther- ‘modynamics are somewhat improved by interaction between Zn” and CI ions (with weak complex forma~ tion), probably allowing strong solutions to be formed with evolution of #,8. Such a route could be interest ing if methods of recovering zine from chloride solu- tions were devised (or, for that matter, if a market for zine ehloride could support such a plant). Reductive decomposition of zine sulfide on the acid side is not considered because hydrogen overvoltage ‘on zine in the presence ofall the Impurities in con centrates is probably too low. On the alkali side, hydrogen overvoltages are lower, and it is possible that Reaction [26] could be exploited, at least on a mercury cathode. There would have to be some direct use for the resulting alkali sodium sulfide solutions. Alkali decomposition would also yield sulfide solu- tions, but the pH values above which zine sulfide would decompose without oxidation or reduction are really in- accessible (see Fig. §). LEAD ‘The Eh-pH diagram for the lead-sulfur-water sy: tem, shown in Fig. 11, contains only one sulfide phase, galena (PbS). However, the chemistry of lead must take into account a strong interaction between Pb" and SO; ions, leading to solid PbSO, at significant concentrations, and an almost equally strong inte1 action between Pb" and CT ions, leading to the crys~ talline PbCk, salt or, at high CI’ activity, to PCL, ions in solution. The effective boundaries of PbS sta- bility in the presence of 1 M-CI” or 1 M-HSO; are Fig. 11—Eh-pHl dlagram for the Pb-S-H,0 aystem at 25°C, Including PbS boundaries at 1 M_ CI” and ab 1 MISO}, Standard conditions; acid section only. 512-VOLUME 78, DECEMBER 1976 shown in Fig. 11. The alkali side is not show in Fig. 11 because it follows precisely the zine diagram (Fig. 9) with the alkati limit of PbS stability at pH value > 16, Consistent with this diagram, it has been shown that ‘an oxidizing leach will yield elemental sulfur and lead in solution in perchlorie, nitric, sulphamie, or acetic acids," while lead sulfate ts produced in ammonia ‘ammoniuin sulfate leaching.” Tt is also known that ‘strong H.S0, or HCI will decompose finely ground galena to HS and the insoluble salts, although there is no evidence that this has ever been considered as a first stage process for hydrometallurgy. There is every reason to believe from Fig. 11 that the Faleon- bbridge matte leach conditions would be favorable both for decomposing galena to HS and PbCls, and for dis- solving the lead chloride in the strong HCI as the anionic complex PbCI.. In excess HCl even insoluble PSO, would be decomposed and dissolved. Reductive decomposition of galena has also been demonstrated.” In either chloride or sulfate systems, ‘galena is reduced to metal, with H,S evolution, elther as an electrochemical cathode, or by means of ‘eathodically generated Cr” ions. The resulting spongy metal would contain all the noble impurities normally present in pyrometallurgically produced lead bullion. ‘The above descriptions and observations cover the three predictable paths for galena decomposition, indicated by the Eh-pH{ diagram. The chemical equa~ tions are as follows. a) Oxidation PbS + 20x— Pb™ + 8° + 20x" [28] PBS + 4H,0 + 8Ox —~ PbSO, + 8H" + 80x" [29] b) Acid decomposition PbS + 2H" —~ Pb" + HS PbS + 2HC1—~ PbCle + HS PBS + HsSO, —~ PDSO« + HaS c) Reductive decomposition PS + 2H" + 2R— Pb’ + HS + 2R" PbS + 2R—~ Pb? + BR +S [30] [30a] [300] (s1} [2] Ihave chosen a rather simple lead process to de- scribe that follows Eq. [28] and uses nitric acid as a source of both acid and oxidant. This process has Deen studied only on a bench scale” and contains serious unsolved problems, from an applications point of view, but it demonstrates some features that can bbe described as ideal. The flow sheet is shown in Fig. * 2. * Galena is one of the few minerals that will react with cold, dilute (1-4 M) nitric acid, and in doing so below about 40°C, sulfur is not oxidized. Lead nitrate is produced without energy consumption, and the pregnant solution can be neutralized to pH = 6 or so for purposes of iron (and perhaps zinc) hydrolysis. ‘The leach itself will become too slow to be useful be- ow about 10 to 20 g/1 free HNOs, but the addition of a small excess* of PbO; in a counter current “Fxceat wth espec oan aid in PAS PRO, aif 9200" + 900 #5 METALLURGICAL TRANSACTIONS Bbe a) i se aaa Do tees Teel awe | |) Coo] Cotes] i cts!) cb wk 5 te Fig. 12-A nitric acid process {or lead concentrates operat » ng t ambient temperature ané pressure. Schematic. 5 ‘with new concentrates leads to rapid neutralization at § room temperature. The purified solution can be | electrolyzed (again at ambient temperature) to yield lead at the cathode and PbO, at the anode. _ “The process suffers from difficulties in the elec- (f] trolysis—a diaphragm cell is needed to maintain a | neutral catholyte, and addition agent technology for lead cathodes of uniform thickness (instead of den- rites) has not been adapted to nitrate electrolytes. Yet the energy requirement is low (less than 400 KWH per ton Pb + PtO,), and there could be a special mar- kket for the anode product if it is available at the nor- mal market price for lead. "There is little Likelihood that this nitrate process for lead is really best, even if all its problems are solved; however it does demonstrate that hydrometal- lurgists may succeed in finding useful processes for ‘concentrate treatment that operate at ambient tem- perature and pressure, thereby eliminating a prime ‘Source of energy consumption and the difficult ‘engineering problems of efficient heat transfer for corrosive slurries. MOLYBDENUM ‘There is not much evidence in Table I that molyb- denum concentrates are a serious source of atmos~ ppheric SO, at least on a global seale. But molybdenite roasters are small, and there is little incentive for exit gas treatment, except perhaps when the valuable and volatile by-product, rhenium, is recovered. Nevertheless, the hydrometallurgical decomposition ‘of molybdenite has been studied with particular reference to concentrates containing impurities detri- ‘mental to the use of roaster calcines in steel-making, ‘such as copper and lead.” "The Eh-pH diagram for the Mo-S-H,O system is shown in Fig. 13, only for the acid region. Although {in alkali solutions there is some evidence for thio- ‘molybdate species in solution such as MoS,O;-« (e=0 to 4), there is no indication that natural molyb- denite can be dissolved in caustic solutions, and ap- plicable thermodynamic data are not available to in- ‘corporate thiomolybdate into the diagram. METALLURGICAL TRANSACTIONS B = vor (suey porenriat Fig. 19—Eh-pl diagram for the Mo-S-110 system under com- pletely reversible conditions. Standard conditions; acid sec~ {on only. After Majima.® In the absence of any thermodynamic indication that ‘MoS, can be decomposed by acid or alkali reagents, only the oxidative and reductive dissolution paths are indicated by Fig. 18, 4 'a) Oxidative decomposition ‘MoS; + BHO + 150x—~ Mo" + 2HS0; + 141174150" [33] MoSs + 11Hy0 + 180x~ MoO, + 2805 + 22H" +1805 34] b) Reductive decomposition ‘MoS, + 4H" +4R—~ Mo” + 21,8 + 4R* (35) MoS; + 4R— Mo’ +28" + 4R*. [36] ‘The reductive decomposition path has not been re- ported and may suffer from difficulties in forming the metallic phase of molybdenum at low tempera~ tares (it cannot be effectively electroplated) and from the low hydrogen avervoltage on any trace amounts of metal that may be formed. ‘The oxidative route as {identified on the diagram also does not look promising because MoOs is poorly soluble at low pH’s, and ‘would form in the presence of leach residues, de~ ‘manding a solid-solid separation. Only the ammoniacal route studied by Kunda and Rudyk” would appear feasible from the thermodynamics. Tn fact, although molybdenite appears to be un- attacked by such oxidants as acid ferric chloride Solutions, exerting a potential of about 0.7 v on the seale of Fig. 13, the mineral is slowly dissolved by weak (1-4 N) nitric acid at ambient temperatures. Unlike galena, all the sulfur is oxidized, and the ob- served stoichiometry is almost that of Eq. [34]. The Gifference is that the cation MoO:” is formed instead fof molybdic oxide. This solution, is, however, super- saturated in MoO, and the oxide is rapidly precipitated in fiber-like crystals (Fig. 14) at about 80°C. ‘This chemistry forms the basis of a proposed pro- cess shown in Fig. 15. The leach is conducted at am- bient temperature and pressure (but in a tightly closed system to recover the reduction product, nitric oxide). A large circulating load of MoS; is car- rried (as in the case of the zine process offered by VOLUME 72, DECEMBER 1976-513,‘Veltman and 0’Kane™) to shorten the residence time required for a satisfactory composition of pregnant solution (about 100'g/1 MoO). The circuit shown deals with the details that close the eireuit, including sulfate elimination (as gypsum), acid regeneration (from NO), rejection of insoluble residues (by clean-up flotation) and purge solution treatment (for removing substances ‘that build up in solution, including valuable by-products such as rhenium and copper). ‘The product from this reaction is free of silica Fig. 14—Scanning electron mieroscope pictures of MoOy:1/2 4,0. Magnification 320 times. tesco esa, 240, Feel a Fig. 15A nitric acld process for molybdenite concentrates developed at UBC. Ambient temperature leaching. Schematte. S14-VOLUME 7B, DECEMBER 1976 ‘and about 100 times lower in iron and copper than. equivalent roaster calcines. It is hydrated (MoO; +1/214,0), and since these hydrates are somewhat volatile, would require a low temperature calcination before their addition to a steelmaking furnace could — bbe considered. Production of molybdenum powder or ‘nonferrous alloys would present none of the problems for this starting material that arise from the use of caleines. My best estimates are that this process may cost about 16¢ per Ib (Mo-contained) in direct operating costs of a 5 to 10 ton/day plant costing about 2 M dollars in capital, but these estimates suf- fer from academic shortcomings and should be re- peated by any serious client. TRON MINERALS In the consideration of treatment methods for sul- fide concentrates, metallurgists are conscious that the tron minerals, pyrite and pyrrhotite, are every- where, and their decomposition chemistry plays a role in process considerations. Fig. 16 presents the Eh-pH diagram for the Fe-S- HO system, with dotted lines filling in the limits of metastability for pyrrhotite of two different composi- tions. The decomposition equations for these two minerals can be written as follows, 2) Oxidation FeS, + (4y + 3)H,0 + 180x~ Fe(OH) + 2807 +(8x + 9H" + 1503" (37) Fo8y + 20x— Fe +5 + 200°. (28) b) Acid decomposition FeSy + 2H" — Fe + HS + (y— US" [ss) ) Reduction FeSy + 2yH" + 2(x ~ 1)R —~ Fe" + HS + 2 -1)R" [40] FeSy + 2(y ~ 1)R = FeS + (y—1)8"+ 2y—1)R* [41] FoSy + 2yR— Fe" + yS* + 2yR" (aa) 6) Alta! decomposition 5, +2,01" FeO, + (2 «2 x +xtho =a) fa] Fes, +200" dre. +ys"«($-a)uo + (%x-$) &s4/3) (44) ‘The iron sulfide minerals in nonferrous concet trates tend to display some unusual characteristics ‘when compared to their nonferrous counterparts; in ammonia leaching processes, pyrite, and to a lesser extent pyrrhotite, are incompletely reacted and appear in Teach residues. This is probably because they are protected by coatings of iron oxide, which slows down their decomposition rate. In acid oxidizing leach- ing, pyrrhotite reacts rapidly, though coarse particles METALLURGICAL TRANSACTIONS Big. 15-Eh-pll diagram of the Fe-S-H,0 {andard conditions metastable boundaries of pyrrhotite eS and Fe,S,) shown in dotted lines nay not quite react completely if the acid strength eclines. Pyrite reacts much more slowly than chalcopyrite in acid pressure leaching with oxygen, and is virtually immune in ferric chloride leaching, bbut reacts more rapidly than chalcopyrite in hot (weak) nitric acid. The reason is not clear, but it may be that elemental Sulfur oxidation can account for the differ- ‘ance; pyrite is one of the few minerals with a molar volume smaller than that of its sulfur content when the latter is converted to the rhomble or monoclinic form. Therefore elemental sulfur should protect pyrite from oxidation under conditions where the sul- {ur itself does not oxidize. Chalcopyrite and other nonferrous minerals would not receive complete pro- tection because the sulfur would not occupy the whole volume of the mineral from which it has formed. In nitric acid, sulfur oxidizes extensively to eliminate this source of protection. Pyrite has also been shown to be protected galvanically to varying degrees by ‘more reactive minerals such as galena, covellite, and sphalerite.”" ‘The mineral pyrrhotite has received particular at- tention in the acid decomposition path (Eq. [39] be- cause dissolution should take place at pli values below ‘bout pH = 2 (see Fig. 16). Yet, experimental results om the dissolution of pyrrhotite in acid have been agued with lack of reproducibility and a lack of inderstanding of fundamental mechanisms of dissolu- ion. There appears to be no difficulty with pyrrhotite of stoichiometric composition, but natural pyrrhotite contains 8 to 12 pet excess sulfur, and Ingraham et «2 attribute the inhibition of pyrrhotite dissolution in strong hydrochloric acid to formation of a protective lm of elemental sulfur. Van Weert ef af” also studied METALLURGICAL TRANSACTIONS B Fig. 11—Simplified flow sheet for pyrrhotite dissolution in an ‘cid treatment of nickel concentrates (after aibiki"), this reaction, paying particular attention to the incu- bation time before dissolution proceeded rapidly, and came to the conclusion that pyrrhotite dissolution was inhibited by a high REDOX potential, associated mainly with Fe" ions in solution. The latter were taken into the strong acid solution by the dissolution of magnetite, coexisting withthe natural pyrrhotite in the sample. Jibiki"* has done a careful study of the dissolution of pyrthotites of a range of stoichiometries in both hydrochloric and sulfarie actds. His findings were that the pyrrhotite in as-received nickel concentrates (and other natural pyrrhotites) did not dissolve in sul- furie acid up fo about 14M or in hydrochlorie acid below 3 M at temperatures of 60 to 80°C; yet pyrrho- tite would leach in 0.1 to 1.0 M FSO, or HCl if one of the following procedures were followed: ) the Dyrthotite is reduced” at >500°C in an Ha/ilS gas Stream containing atleast 10 pet Hy: b) the pyrzhotite ‘is subjected to cathodic reduction during acid dissolu- tion, or; ¢) the lump natural pyrrhotite is crushed and ground in an inert atmosphere, with no opportunity tobe exposed to air before dissolution in deaerated acid. These resulls lead to the conclusion that the in- hibting factor for dissolution of pyrrhotite in weak acid is an invisible film on the surface caused by ex: posure to air, which particularly affects the sulfur- rich natural pyrrhotites, but plays a negligible role for the more stoichiometric compositions. Since standard nickel concentrates from the Cana~ dian Shield ore bodies are predominantly nickeliferous pyrrhotite, Jibiki™ proposed a process for upgrading Such concentrates and sltimately treating the pent- Tandite-chaleopyrite product for nickel and copper re- covery. The simplified flow sheet \s given in Fig. 17. SULFUR AND ITS DISTINCTIVE CHEMISTRY In the direct leaching of sulfide minerals, it is mown that sulfur does not readily oxidize to sulfate in spite of high oxidizing potentials, and sulfate does not readily reduce to lower valence states in spite of strong thermodynamic driving forces, i.e. at the cathode of a zine or manganese electrowinning cell. Furthermore, in ammonia leaching, intermediate forms of sulfur are formed, notably thiosulfate and polythionates. It is useful to examine the Eh-pH dia- gram for the sulfur-water system with the sulfate forms delected (Fig. 18) to determine the range of metastability of these intermediate valence states VOLUME 78, DECEMBER 1976-515Fig. 18—Eh-pl diagram of the $-H0 system at 26°C if sul- fate formation is irreversible and remaining sulfur redox systems are reversible, Standard conditions. deriving from the failure of sulfur to oxidize com- pletely to sulfate."* "Ths an aici way to Bing he despre henodymamis of the Bp dagam ino pement wi cbervations hat contain ely herp abaned. Pen ~“This diagram correlates rather well with some of the observed reactions of sulfur compounds at high pH values: ) Sulfur dissolves at high pHs in sulfite solutions to yield thiosulfate: 803 +S — 8:03. ‘The observed speod of this reaction obscures the mechanism for ammonia pressure leaching of sul- fides, where thiosulfate seems to be the precurser of other sulfur species. This reaction is reversed in ‘acid solutions because of the formation of sulfurous acid: [45] S,0; + 2H" — H,80, 48°. (a6) ») Sulfur disproportionates in alkali solutions to yield both thiosulfate and sulfide ions: 4S° + 6OH' — 8,05 + 28° + 3H,0. (a7) ‘This reaction appears tobe favorable ony a fairly high pH values (pH > 14). ¢) Sulfur dissolves in weak alkali solutions (NH,OH or Ca(OH), slurries) to yield polysulfide and thiosul- fate fons: 125° + 60H — 8.05 + 285 +3140. (98) “The polysulfide fon has a tny area of stability inthe metastable Eheplt diagram (Fig, 18). This lat reac tion appears to be the most useful for applications where an inorganic leach for elemental sulfur is de- Sirable. Acidification of the resting solstion should eprecipitate the sulfer 25; + S05 + 6H — 128° + m0. (9) In fact, although sulfur is extensively precipitated, 1 fraction of it remains in solution as a very complex S16-VOLUME 7B, DECEMBER 1976 Aistribution of sulfur compounds (Wackenroder’s Liquor). ‘CONCLUSIONS ‘The direct leaching of sulfide minerals associated with nonferrous metal concentrates of copper, nickel, zine, lead, and molybdenum is a demonstrable techni- cal option in the recovery of these metals, even though there are still only a few plants in existence and that conventional smelting with stack gas SOs recovery remains the main processing method under consideration today. The incentive for direct leaching remains compelling, and the chance of success is good for eventual development of fully competitive hydro- metallurgical plants for all five metals, for the follow- ing reasons: 1) Direct leaching of sulfides leads to elimination of air pollution by $0, as demonstrated by every existing plant and pilot plant. 2) Hydrometallurgical processing cannot guarantee avoidance of land and water pollution by residues and purge streams; however, it is easier to control ‘these small volumes and keep them out of the environ= ‘ment than to control large volumes of gases without leakage to atmosphere. '3) The preferred product form of sulfur is el ‘mental, because it is directly marketable. HS is ‘easily converted to elemental sulfur, so is next in preference. Sulfates, when formed, cannot easily be converted to elemental form, and must be disposed of in the environment as gypsum, or jarosite, or as am- monium sulfate having value as a nitrogen fertilizer ‘on alkali land. Elimination of sulfate solutions in ‘sewer streams is potentially dangerous, and should be restricted. 4) The fuel value of elemental sulfur is only avail- able hydrometallurgically if it is oxidized to sulfate, ‘as in ammonia leaching. Tt would be better to abandon this fuel if sulfur or 1:8 can be obtained instead; the leaching aspect of hydrometallurgy should be designed with sulfletently good heat exchange so that this fuel value is not required. 5) The energy requirements of hydrometallurgical processes, although beyond the scope of this paper, are not intrinsically larger than those for pyrometal- lurgy and where evidence seems to exist for high energy requirements in hydrometallurgy, the prob- Jem is mainly one of technical maturity in the pro~ cesses, rather than one of fundamental inefficiencies. 6) Every extractive metallurgist is willing to ac~ cept the best technology, whether it is pyrometallurgy or hydrometallurgy. However, in this last quarter of the twentieth century, and for these five metals, I believe that hydrometallurgy offers some powerful in- centives and may well pick up the action of technologi- cal progress as our knowledge of the options advances. ACKNOWLEDGMENTS ‘The special contribution of my colleague, Dr. Hiroshi Majima, now of Kyoto University, Japan, in originally introducing me to the Eh-pH diagrams for ‘minera} systems” is gratefully acknowledged. This paper also acknowledges many contributions to hydro- METALLURGICAL TRANSACTIONS 8metallurgical processes that are not mentioned in the Uist of references, but that are important contributions towards the advancements to which references have ‘been made. 7 REFERENCES 1. FA, Formed “Ammonia rs Lesh Proce for Reovtng Nik Cop: ‘eis and Coat fom Sheet Gordon Nickel Sulphide Concent ate,” CM Tune 1953, 1 56, p37, Ssh FA. Forward andV.N. Machi: J ‘et, 1955, v.79 457 2 Kae A nd "ten op * Ga sin Me. Ba, 1974, 7 9p. 62.72. 2.9.6, Thom Wap, 2nd . Van Wee The Fonte Matte Lech Proce" Mei, 1971, vl 23,90; 7, 99.1318 ‘4D. J Joes “The Leaching of Clcopyt,"PhD. Theis, Department of ‘Metal, Usvrsty of Bash Columb, Mey, 197. S.P-J-McGadey.P-A. 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Valent: “Geer Chemisty," Alar of Blcrochembl Elsi ‘Agucus Solution, M Postback 2. p. 6, Pergamon, 1966. 36, 1 Maj: Unpaid pl aga DECEMBER 1976-517