Critical Reports on Applied Chemistry Volume 1 Topics in non-ferrous extractive metallurgy Edited by A. R. Burkin Published for the Society of Chemical Industry by Blackwell Scientific Publications Oxford London Edinburgh MelbourneCritical Reports on Applied Chemistry: Editorial Commitee CoA, Finch Hi. Egan AS. Teja ‘Chairman CR. Ganellin PB. Tinker ALR Barkin 1D. Morton A. L. Waddams G. A. Davies HD. Kendall LRH. Wooldsiége (© 1980 Sacay of Chemica ndusey ‘Typeset by Eset Lt hd pubs forte Musomer Nevin, Bath, Hlnlvl Scribe Batons Peta in Gree stn 2 Eel tie Biting & Sons Lie, Gulfort ‘ney sad, Oxore,OX2 EL, snd bound by $n Steet, Londo, WEIN ES ec Hal Binder, oxford $ Foret Rod, Edinburg, EH 20H 52 Bescon ste, Boson Dsinuted in he US.A nd Canta Msscharent 108 USA yaa Pes 1d Se, Cron 2 Division of Sehn-Wiey & Sons ne. ‘stoi 05, useala Kew York rit rere No par his tin Lira pubinon ny be repro, sored Cologne Pabtition Date In retiea eye or ears, Shy form oy ay me Scouinecrotiewi thou a {.BurunsAlsod Rebar, Sey of Retoet te me pomision of ‘Chemie dary Sens be copy owner oo Tae Fist posed 1960 ISBN os2006i8 “opis in nonserousexactve metre. ‘(Cee reports nape chemi TC Noofereur metie= Meta 2 BL Contents Tntroduetion Extractive metallurgy of copper Gunnar Thorsen Department of Chemical Engineering, Norwegian stitute of Technology, Troi ‘The extractive metallurgy of deep-sea manganese nodules ‘A.J. Monhemius Department of Metallurgy and Materials Science Inperial College, London Extractive metallurgy of uranium ‘A. R. Burkin Department of Metallurgy and Materials Science, Imperial College, London ‘The electrolytic production of zine A.J. Monhemius Department of Metallurgy and Materials Sclence, Inperial College, London IndexEditor’s Introduction \Wester eivisation depends on three great primary industries, production of food, production and utilisation of minerals, and the provision of energy. These are Closely interdependent and each i said to be moving into a stage of being unable to satisfy world demand, The reviews contained in this volume are concerned with methods of producing certain metals from mineral resoutces.1t is fiting that they should be published under the euspees of the Society of Chemical Industry because they show the rca efforts which have been made in recent years f0 improve existing processes fad to devise new ones which, in many cass, involve chemical restions whieh have ‘never before been used in extractive metallurgy There are several reasons why changes in the technology are necessary. The first is thet growing restritions onthe discharge of gaseous, liquid and solid wastes from metallurgical plants make them essential. The second is that it s becoming necessary 19 use ofes Which cannot be economically treated by proceses used conventionally at preset, anda thirds that anew process or change in an existing fone may improve efcieney under some, if not all circumstances. is frequently stated hat the world’s reserves of ores of some metas are ‘becoming exhausted. Such an assertion ins particular case requires large amount of factual end technica! justifeation before it can be accepted. An attempt has teen made to show what happens when supply and demand for & metal are ously diferent, inthe review dealing with uranium, Tn some eases exhaustion of reserves equated to diminishing reserves of high grade sulphide ores which can be treated in modern smelters. Copper smelting foviinally used hand-picked lumps of ore. As this became impracticable the Froth fotation proceis was introduced early this century, producing high-grade con- ceniraes on which modern copper smelting practice has been developed. As the trade of sulphide ore avilable ia a mine becomes lower, the cost of mining and rrling it beoomes higher per unit of copper contained in the concentrates, until the economic eof grade is reached, when production stops. The copper sulphides remaining in the ore-body are then no longer en tual reserve of copper ore unless Cither the real price of copper rites or « new or improved process is introduced ‘which makes it posible to resover the metal from it economically. This provides {he incentive to work out methods for treating low grade sulphide ors. ‘A different requirement i to develop processes which use the so-aled ove ‘ores, Thus most of the known reserves of nickel occur in the form of slieates, the Tatrite ores, whereas most of the nickel produced today'is obtained from sulphide Editor's Introduction = vii lores. A change to latsrites must come in due course and the major nickel product ‘companies have been developing new or updated processes for treating these ores. ‘The recovery of metal values fom deep sea nodules would be another example of treating a new source, should they ever be “mined? on a signifeant scale ‘Some copper sulphide ore bodies have been subjected fo weathering at the top dive to seacton with water containing dissolved oxygen, Over geological periods of time this caused the formation of an ‘oxide cap’ containing copper in various minerals other than sulphides, as well as the distribution of copper over areas round the ore body due t© represipitation from ground water. Only Timited ‘mounts of oxide ore can be fed into a smelter cogether with the sulphide oration oncenirates so that most of it sae an snused potential sores of copper ‘The solvent extraction ~ elestrowinning process which was proved to be com- rially successful in the late 1960's is now being used to recover copper from these oxide ores. In the process an organic chelating ligand, of «type described ‘below i uscd to selectively extract copper from an impure acidic aqueous sulphate solution, into a hydrocarbon diluent. The copper ie stripped from the organic phase bby a more stzonsly acide solution of copper sulphate coming from the electrolytic tank house, to which it returns with is copper content increased. A number of plants vere built ro use this process, one in Zambia to tret 14,00 gallons per Irinute of impute copper-containing rtution. Others were planed but the fll in the price of copper caused portponement of the introduction of more production capacits, ‘Any kind of ore containing copper can be used to feed the solvent extraction ~ lectrowinning process provided that its copper content can be dissolved so a5 to produce an acidic copper sulphate solution. Ths includes low-grade sulphide ores from which concentrates caanot be made evonomiealy, and waste rock from the mining operations, The heaps of material are terraced and sprayed with the leaching ‘olution which is collected at the bottom and treated for copper moval before being returned to the heap. The oxidising agent which i required to leach the sulphides is ferric sulphate, whieh is produced from the rock, and the whole Teaching and oxidation sequence of reactions is sreatly accelerated by the naturel pretence of crtain bacter ‘The progression fom heap and dump leaching has been to leaching the rk fnesty, without mining iat al. This has been done in the case of copper ores by fracturing the low-grade ore remaining efter mining using conventional explosives “his tecinique has also been used on uranium ores and fr these, «later develop: sent has been to lech porous sandstone deposits containing uranium without isturbing the ground at all except for drilling a pattern of holes to inject and recover solutions. It seems likely that in later stage of technologial development Docks of ore will be fractured and he surrounding rock used as @ container in Which pressure leeching willbe cartied out to recover the metal value,viii Editor’s Introduction [At the same tim as development ofthe use of low-grade and new types of ores, _work on new proceres to teat conventional ores and concentrates has been going fon. Those concerned with copper sulphide concentrates, dealt with in this volume, ‘would be in direct competion with smelting I is certain that in a aege sale ‘operation smelting wil be moze cconomie thas any hydrometalluricl process for the treatment of concentrates i considerable quantities of sulphur dioxide may be Sischarged into the atmosphere, As emission eontrols become more stringent, and fo more expensive to meet, 0 the eiference in cost will essen. For a smal sale ‘operation a hydrometallrgical process might in any ease be more eeonomi than smelting ‘One ofthe incentives to develop new processes for treating copper concentrates vas the bei that they would be “polluton-ee’. This is not the ease, but one fndvantage of some of thei fs the fact that in certain ofthe new processes some at Teast ofthe sulphur content ofthe ore can be recovered in elemental form. It might flso be thought that pyromtallurgiee process would require the wse of more ‘eneray because they Work at high temperatures. However, most of the heat ‘btained by oxidation ofthe sulphides, wheres the energy required co pump solu tions in hydromsetallurgical processes is very considerable "nthe eases of many other sstals new processes have been introduced into the ‘overall flowsheets, These often involve solvent extraction and ths technique is hneving a very signifiant effect on non-ferous extractive metallurgy in general T ‘vas fist use i the uraniom industry and by the mid 1960s it seemed that t would hot exid beyond that. Is use in copper recovery caused it to be looked at again tnd it was realised that in chloride sluts some metals can be made 10 orm snionic oF uncharged species which peemits their separation fkom others whieh remain as cations inthe same solution. Uranium forms an anionic complex in Sulphate solutions and it was this fact which led to the use of fon exchange and solvent extraction in its recovery and purification, Increasing understanding of solvent extraction and the solution chemistry of| setae in genera, among those working inthe field of hyrometallrgy has fe 10 fhe development of numerous processes which can be Std into overal owsheets. “These do mot sem to be know to anyone exerpt those atively working i he fl. Ie sin the bli that they may be of interest 1 many other chemists and engineers thatthe three authors of the reviews contained here have written them, Sargon [As one of thote chemists the Fdtor of the Society sid that it would help if some ofthe more obscure terms sed in the text were explained. Most of them could not be replaced by other words without making the text appear strange t© people soquaited with the fields of hydrometallargy and mineral processing, and tis hhoped that some of these will read it, Explanations ate given below. —— ‘The sizeof particulate solids i expressd as a range of sieve mesh sizes, These sizes were formerly given asthe number of wires tothe inch but are now usualy expressed in micrometres. Thus +74 em means thatthe particles are larger than “Ham of, more socurately because of their ircegular shapes, they will not pass through 4 200 mesh soon which has Roles defined in tables as 74 jm. —74 jin particles wll passthrough a 200 mesh sereen. Although it may seem ode speak fof particles of size about 74 jm, the number Is given as it appears inthe table of Teaching of particulate ores is frequently caviod out in pachuca tanks. These vericl cylindrical tanks with a conical bottom, air usualy being introduced {hrough the bottom point ofthe cone to cause agitation. A mechanical sree may also be used if ae alone does not give suficiont mixing to prevent solid sepacating ‘ut. The height of tank may be 10 meres of more, with similar diameter. ‘After leaching, the solution # known as the ‘pregnant’ liar. statement that a particular element ‘reports! in the leach residues means that itis found in the residues after leaching ‘A number of proprietary extractants for mals ate referred to in several places in the text. The chemical nature of the materials is believed to be a follows, LIX reagents fom General Mill ne (now Henkel Corporation) Lx 6 Lx 6aN +LIX 63 LIX 70 Has Cl adjacent to the OF on the benzene ring above, KELEX reagents from Ashland Chemical Cox Biter’ troduction ACORGA rogets from pera Chemical Indus Lad (Acorga Lid) pr rt 5 OQ) oe sure Execan Cr with the Eton, 1 ft that he looked ing in mining and commiaution’ Fil, when iehing al these mates ‘uitesorey when I wrote mca on ei In ple of "tramp ioe 1th gut 1979 ALR Barkin Extractive metallurgy of copper Gunnar Thorsen 2 Prometric! yrosesing of copper supe concentrates, 3 21 Conventional processes. 22 Mad proces techies of copper smeking,$ 23 Thewoncna proces? 34 The Noranda rose 8 25 The Mitubisht proses, 26 Which process 1 choose? 10 2 Hydromealaraioa processing rts for copper, 1 3a Vat leeching and aptton leachiag of oxiued copper ree, 13 32 Hyeometairay for eopner concentrates, 16 33 The ShoniteConinco praca, 17 3541, Selective leching and removal of ro, 17 332° Irom selection, 20 323 The copper winning circu 20 34 The Cymer proses 2 BS The Cyprus proses 23 351 "Revotey of by produets and ron cseton, 25 36 Tho curan process, 26 AGI Regineration and rection of ion, 27 37 The Minimet Recherche pres, 28 LIA Rejection af ron, 29 38 Processes using nite eld In sulphate systems, 30 39 The Alter process 34 310 Acsiontre asa complening agent fr coppee, 36 S11 ——Meatiag te ron problem by tshnigues of solvent extraction, 38 ‘ Referees 39 1 Introduction One could hardly think of producing any review on non-Ferrousextractive metallurgy without taking into account the metal copper. Although hooks, reviews, and special isues on copper have been numerous in recent years!" the ever changing conditions, particularly in the energy and environmental aspects of modern industrial activity ~ not to mention the political impact ~ seem to make a venture into the world of copper always worth while. Even for those who follow the ‘copper scene from the ringside there will alvays be something new to add to the story. ‘The new matters do not necessarily need to be innovatory in nature, in the emeeeet ena et ee2 Gunnar Thorsen findings and previously suggested processes may reveal some approaches which could well turn ext to be of importance and interest under preseat circumstances, ‘One aspect of the production of copper is concerned with the basic choice between pyrometallugical and hydromstallugial routes. The traditional pyro retallurgical production by copper smelters became, more or les overnight, the bad wolf in the environmental and conservation discussions which arose io the sixties. twas true that no breakthrough had been made within the copper smelting industry which could enable the new regulations on sulphur dioxide emissions to be met, at least not without enoraioue investment which most ofthe indsty isl? vas notable to make. However, new technology was on its way ~ the pyrometl lurgists were put under pressure and innovations, largely based upoa the principles offlach smelting and continuous processing, were launched. Although sl ina state of development, the first new technology sieliers are now in operation In the meantine, the hydrometllugical approach to copper processing has seccived & lot of support. Fromm the environmental poi of view this appeared to be the answer to avoid pollution problems. However, the hydrometllrgica! processes have pollution problems of their own. Problems associated with pas fission may appear to be nonexistent, but plant efluents inthe liquid and solid fates may le! to serious contamination of the envionment if aot taken care of properly and quantitative. Usually there are technical solutions avalable, but gain the investment and operating costs may be considerable and may even prevent an overall poft being made This eview on the extractive metallurgy of copper is nat intended t0 be comn- prchensve, attempting to cover all aspects of the activity taking place at he retent time in the field of eoppst extraction. Rather, i wil be sletve and an tle has been made 1 present the main ideas reflected inthe various processes actually in operation or being developed. Obviously, a number of parallel developments are taking ple in diferent plant and laboratories around the world. Inthe hysrometalueical processing oF copper concentrates, for instance, the chloride leach routes seem to be much favoured. In the pyrometallurgcal fold, on the other hand, there are several sillrent kinds of approach being made to try t0 integrate the rosstsmeling- converting tepsinto an autogenous continuous process, The differences in approach appear mostly tobe found ia the engineering echniques and desig ofthe reactors rather than in the process principles ‘The descriptions of processes outlined in this review will for obvious reasons Ihave tobe based on published data oF other iaformation at hand. From the vast mount of material published during recent years it will elways be a mater of Opinion and taste as to wat to take inka eansdertion, One exterin fo selection could be the depree of simplicity inthe processing ctcuits. Elegance in extractive retllurgy, a in all incstrial processing, appears as chore cue which minimise Extractive metallurgy of copper 3 the route from ray" materials to products, In addition the possibilty of complete Utlzaton ofall components present in the raw materiale will always find favour, Its believed that important key Factors in the present and future processes for recovering copper from base materials, ie. ores and concentrates, will be the handling of the main by-products, ron and sulphur. Special attention will therefore be paid to the ways in which these components ae taken care of, ether by disposal and rejection or, bette, by making useful and salesble products from ther ‘The basic copper extraction industry has traditionally used two main ap- proaches: pyrometallergical and hyydrometallargical processing. It is to be noted, however, thatthe general trend of modern extractive metallurgy tends to integrate these approaches. This i relecod for instance im the roas-leachvcletrowin peo ‘exstes for both copper an se wherein the front-end ofthe Rowsheets the roasting step isa typical pyrometallurgcal stage while the leaching of the ealeine product fand further slctrowinning of the metal values belong to hydrometallurgy. At the far end of the lowshect the techniques of pyrometallurgy may be revived, a6 for instance in the process for smelting ofa leadsilver rsidue.® In the copper industry, however, a pyrometallurgcal proces has a distinctive feature and meaning in thst the copper ix produced in a Tarnace as liquid metal (iste copper). Basically in this review that cutline and definition willbe followed. 2 Pyrometalturgical procesing of eopper sulphide concentrates ‘About 90% of primary copper production is from sulphide ores, which contain from 0°5 10 2% Cu in the orebody. After concentration by froth flotation the resulting copper concentrate will contala from 20 40 302% Cu which willbe the typical starting point Fors pyrometallrgical smelting process ‘The pyrometalursieal process may be divided into the folowing three steps: 1 Roasting. Sulpsur will be partially eliminated as SO, by partially oxidising the sulphides at $00-700°C by reacting with ae 2. Maite smeling. The roasting product is melted together with a silica fox at About 1200°C, forming 4 liquid twosphase system consisting of sulphide phase {onstte), containing virtually all the copper, and a Tiquid sisg phase containing silica, alumina, ion oxides andl other minor oxides with ss low copper eontent 35 possible 3 Converting. The liquid matte containing copper and iron sulphides is oxidised ‘with aie wheceby the converting reactions take place in to sequential stages: () the Fes elimination stage, i DPS 4 30, + SiO{ux) + 2Fe0.SiO slag) + 250, (i) the blister copper formation Cus + 0,200 +80,4 Gunnar Thorsen, ‘An essential feature of the converting reactions is thatthe segond reaction ~ the blister copper formation ~ dacs not start before there is only about 1% FeS le in the matte? Tt il be seen that steps 1 and 3 rolease sulphur dioxide. Both steps are con trolled oxidation processes, however, and in modern copper smelting practice the demand forefiient $0, recovery has to be adequately met. The concentration of 0 in the fluent roaster gases high enough (5-15% for it to be efficiently used for production of sulphuric eid, op even reduced to elemental sulphur. Furthet= ‘ore, the oxidation reactions may be catied out using oxygen enrichment. In this ase the energy wed in heating the nitrogen in the eluent gas when ae is used for ‘combustion is sived. The main elect of oxygen enrichment, however, is to increase the $0, concentration. In the INCO fish smelting process, which will be dis- cessed later the content of sulphur dioxide inthe eluent gases may bess high as 80% $0, Obviously, this san excellent source for production of liquid SO, or ‘clement sulphur. 21 Conventional processes “The conventional practice of most copper smeltes has been to carry out the three steps of roasting, sling, and converting in separate operations. The roasting, ‘which is an optional step, is often practised prior to smekking withthe purpose of utilising the released heat to dry and heat the charge before it i alded to the smelting furnace. This operation will result ina considerable saving of fuel in the smelting procses and also increase the eapeciy ofthe smelting furnace "At the second stage ~ mate smeting~ the real challenges to smelting tech igues are th following reqizements: 1, the abatement of the SO, emission problem; 2, minimising the fuel and enetzy requirement 3, section of wast sg phase sufcintly low in copper. "The conventional and widely used practice has been to use a reverberatory furnace to carry out the melting of the mixture of copper concentratefealine and the silica Hux, The heat for smoking and maintaining the temperature of the wvo- phase Higui rster of matte and slag at about 1200°C is provided by combustion Of oil natural gas o pulverized coal. The hot combustion gases sweep and pass lover the charge ‘Apart from the considerable consumption of hydrocarbon fuss the inevitable oxidation of sulphides in the sielting furnace will result in a serious pollution problem because the SO, in the smelter effluent £283 is too dilute (1-2%) for Feeovery &8 sulphuric scid. In modern reverberatory plants which usually are provided with « flu-sold roaster itis possible to reach 90% sulphur recovery tvthouttreatinent of exhaust gas from the smster*, Although an overall 10% Eission of SO, might be tolerated in some remote ateas even inthe Future, it rnot believed that any new reverberatory furnaces will ever again be built." Extractive metallurgy of copper s ‘The problem of $0, emission can be solved by wsing an electric furnace for smelting. The heat for melting is generated by the eeericalzesistance ofthe sl. passing electric current between carbon electrodes immersed in it. The quantity of effluent gas wil in this case be rather small and the SO, concentration eam really be controlled by adjusting the air entrainment into the electric furaae. ‘The electrical energy is used eficiently and the eletrie furnace is very versatile and flerble for the treatment of all materials. The major disadvantage is that lectricity tends tobe rather costly, depending on the area of location. ‘An important polat to consider in the matte smeking stage is the copper content ofthe slag phase. The copper concentration in the discarded slags varies from 02 t0 1% depending upon the particular type of operation! Minimum solbilty of copper is obtained by keeping thesliea concentration i the sag elose to saturation. This wil also kep the mattesiag missbiltya¢ «minimum, Further ‘more, the formation of magnetite, FejOy should be kept a8 low as possible by avoiding excessively oxidising conditions. Magootite wil increase the viseosity of ‘the slag, thereby making separation of the ewo phases more dificult, ‘The purpose of the converting stage for the coppet mate Is 10 remove ion, sulphur and other impurities from matt, thereby producing liquid metalic copper ‘of about 98% purity (Blister copper). Convert slags contain from 2 49 15% Ca land have to undergo treatment for copper recovery, usually by Troth flotation of the copper fom solidified and slowly eaoled slag. 22 Madern process techniques of copper smelting ‘An overall energy balance for the copper smting process shows that considerable {energy is obtainable by complet oxidation ofthe sulphide charge. Ths the trende in moder eopper smelting re t make full use of this energy source. Elfrts are also directed towards making the processes suitable for continuous operation, ‘The first development along these lines was the intraduction of flash furnace smelting which makes considerable se ofthe sulphide-combustion eneray for the melting of matte and sag. Thus the eatment of shaloopyrit by fash smelting cia be represented by th equation: 2CuFeS, + 520, + SiOx) Cu, FeS{matte) + FeO. SiO,(Slas) + 280, + heat “The fash smelting technique has been developed on the basis of two diferent principles: 1 The INCO process which is made completely autogenous by se of commerial ovygen. 2 The Outokumpu process which wses preheated air in some cases with onygen tnrichment. Hydsocarbon fuel hae to be added inthis process to make up forthe eneray diference,= ‘Gunnar Thorsen Biswas and Davenport have presented and dlscussed the two processes at length. In a comparison of them, they state thatthe major difference of importance is that the INCO process relies completely upon oxygen to make jt gutogenous hile the Ovtokumpu process uses oi to make up its thermal deficit. On this bait the INCO process will have several advantages over the Outokumpu process ¢ ithas a much lower overall energy requtement; ' inthe absence of niirogen and hydrocarbon combustion produets the volume of ‘elven gas is small and consequently the gas-ollecton equipment i sll; ‘the S04 concentration in the combustion gases ofthe NCO proces will be as Iigh 28 80% which cbviously maker them well suited for further processing to sulphuric i, quid SO, or elemental sulphur; 1 dust losses wil be low due to the modest volumetric low of gas; « throughput in the same size of equipment wil be about 30% higher in the INCO process than i the Outokumpu proces. From the later developments® it has been noted that oxygen enrichment has been introduced in the Outokumps proses. Is further reported that one trend in the metallurgical development of fash smelting has been towards the continuous production of highgrade matte or blister copper. By this means batch eonverting hnas been reduced considerably or even eliminated in some cases, depending on the concentrate materi. similar approach of integration of smelting and converting has also been reported recently by INCO" when a pilotplant eampaign was undes taken to extend the oxygen fash smelting technique to a Smaller smelting unit which ‘would permit smelting and converting in a single unt without fuel requicemeats These later developments in the INCO ang Ostokumpa fash smelting pro- ‘cesses indicate the general modern tend towards a fully integrated and connote ‘operation ofthe roastingsmeling-converting steps in pyrometallurgial extraction ‘of copper from sulphide concentrates, ‘A-continuovs operation seems particularly attractive from the pot of view of sliminating the conventional separate tapping operations in the batch process In the approach of combining the roasting, smelting and converting steps into one fornaze or reactor, however, obviously the engineering and the design of the Feactor will be of the utmost importance, In this context the thermodynamic analysis ofthe QS proces for coppermaking' i vxy instructive and valuable. It hs been shown by this analysis that an efclent operation ofthe single furnace reactor requites the establishment and contralof gradients in oxygen activity by a stagewise introduction of oxygen and solid feed materials along the reactor, A Scliematie diagram of the staging in the Q-S converter is shown in Fig.l This ‘ode! takes into aecount the thermodynamic conditions for an optimum quality ofthe copper meta! product. Of parccular interes isthe thermodynamic discussion ‘of deconverting and slag cleaning in ordet to produce a discharge slag suitably low in copper (for example 02% Cu). Extractive metallurgy of copper 7 coe | 35 Se ig. Schenatie dlagram of taping ia 5 proses ‘Three continuous processes actualy tried in operation are presented in the following 23. The WORCRA process In continuous production of Blister copper from matte in a single furnace, three Tiguid phases will be present: slag, matte and blister copper. Fig. 2 shows the furnace used in the WORCRA process (named after the inventor HH. K. Worner and Consine Riotnto of Austelis Li, Sa fe pa a saat Pg. 2. The WORCRA proce ple es ‘The concentrate and fux re introduced in the mildly oxidising smelting zone The matte and slag fow coustercurzently and in a slag cleaning zone the copper concentration in slag is reduced to about 0:5% Cu, This comparatively low con ‘exntration of copper is accomplished by using rather large part of the furnace for ‘the slag cleaning zone. To keep the temperature at the appropriate level, hydro.$8 = Guanar'Thorsen_ cathon fuel is burnt inthe seting area I sto be noted that the copper concen {tation ofthe slag may be lowered down to 03% Cu by the addition of pyrite to provide further reducing conditions inthe slag cleaning zone ‘Athough the combustion gases from the slag cleaning contain only 1-2%% $0, the high-strength gases obtained from the oxygen enriched oxidising zone make the overall SO, concentration suitable for sulphuric acid production. In spite of the energy requirement the WORCRA. process undoubtedly ap- pears 10 be very promising, partialaly because the slag phase may be directly Fejected without milling and relating. However, the process has so far only been ‘operated ina pilot plant which was closed down in 1970 24 The Noranda procest ‘The only one-rnace continuous process for making blster copper actually in industrial operation seems to be the Noranda process. Fig. 3 shows the Noranda ‘which has mach in common with an ordinary elongated converter The Extractive metallurgy of copper 9 sulphur which has to be removed in a separate stage. The slg from the reactor contains 8-10% Cu which is recovered by milling and froth ftation operations, ‘he final tilings containing 0-5%4 Cu, Further development by Kenneeott Coppet Corporation! has cleaned the slags from 4 Noranda Reactor t902-03% Cuinan ‘lectrcal farnace which employs mechanical mixers to promote magnetite redue- tion and copper extraction at high rates, 25 The Mitsubishi proce ‘The advantage of the countercurrent principle of the WORCRA process has been met in the Mitsubishi development whichis true overall eontinuows process for the production of blister copper from concentates3® The Mitsubishi process loperate with three furnaces, one foreach ofthe three metallurgical stages: sete ing, converting, and slag cleaning. The Furnaces are interconnected as shown in Fig. 4. The melted liquid phases low by gravity in continuous overflow between the furnaces, OCR im Fig. 3 Norinda rate reactor charg with concentrates an fax atone end where the sliss ae heated wth a burner fuse and the smoking takes place whan ar or oxygen-cnrched air is insted into the mate Iyer. Slag and matte move along the reacior with the aijosygen blowing through submerged tuyere, the converting taking place con tinuously along the reactor. The blster copper is tapped from a “well at the bottom and the sag tthe far end ofthe reactor. The high $0, concenteation ofthe gas which is efcenlyeolected by s hood srrangement isan advantage of the process. However, the simplicity of te one stage proses, being more or less tthe condition of equilibrium, has to be paid for by the low quality of the product, The blister copper contains as much as 1-2% concent, ruse #99 rr © | ies Serio foe Converting slog caning “haroce she Fig. Scherat view of the Mui continuous araac ‘This rangement allows some flexibility in choosing optimum conditions for the oxygen potential which should be higher in the converting stage than in the smelting stage to minimise the copper loses, To operate the process under optimum conulions, the variables have to be strictly controlied.* Ths is done by an advanced feed-forward automatic controt sytem. Beetuse there is only one reaction zone in each furnace this will allow a igh smelting rate. Accordingly there isa high throughput in the systenn which is of advantage for the overall heat balance.10 Gunnar Thorsen “The rete slag from the electric slag cleaning fornace will contain 0:5 % Cu “The by-product slag from the converting furnace which contains 10-18% Cu is solidified and reeyeled to the smelting furnace. Its 10 be noted that no sien is tuded tothe converting furnace which keep the recjele small Of maforimportanee, however, i thatthe silia-eee slag inthe converter is basi, thereby lowering the sulphur conten ofthe bster copper to 0-1=0:9% S. This is to be compared to the single-stage copper quality of 1-29 $ which s obtained in the Norands process, 26 Which process choose? ‘This question can never be answered definitely without taking into account numberof local and specific conditions associated witha particular situation. The fav material hos to be analysed carefully, but in metallurgical processes une Cnpected surprises, caused for instance hy the behaviour of impurities, may aie In this context itis reported! that the Bster copper produced by a continuous onesfurnace process tends fo contain more antimony, arsenic and isrmath than the blister copper produced by conventional smelting and subsequent converting. The reason for this seems to be thatthe sulphides of these elements are extracted into the metallic copper alvaye present i the one-stage operation. Inthe conventional converter the Impurity sulphides willbe volatlised during the converting before the metallic copper stars to form. ‘Texasgull Canada is presently constructing a new copper smelter at Timmins in [Northern Ontario which was expected to start up in ate 1979. Ina very interesting and detiled deserption ofthe design development which includes a tnorough txamination of alterative procestes and plant visits all over the work the major reasons for selection ofthe Mitsubishi continuous smelting process are given and ‘nay be summarised as follows: : tried and proven, bis operated for some time on a commercial sales {not labour intensive, successfully automated with furnace fed, air, oxygen, and fuel inputs being computer controlled: «¢ molten furnace products merely overflow with the conventional separate tapping ‘operations eliminated; 1 capital cost competitive with that Fora conventional ar fash smeling plants 1 advanced technology not likely to become obsolete a the next 10 0¢ 20 years; {high quality of blister copper produced and a low-copper slg dseardeds 3 999% 80, recovered as sulphusie acid, 200d environmental catrol and working Conditions are expected, few manual metallurgical techniques are required Tn a comparison of continaous coppersmaking processes Biswas and Daven= pon? state that the difference between the Noranda, Worera and Mitsubishi prosesses are due to the method of injecting the air (or oxygea-enrched st) into the matte, After a discussion of the various problems associated with the various methods, thet conclusion i that only time will tll whieh is the best. Extractive metallurgy of copper =I ‘There sno doubs sha the development witia the pyrometallursical routes foe ‘treating copper sulphide concentrates has been brought coa very advanced techuo~ logical level within the last decade. For a reasonably uniform concentrate of chalcopyrite with a high content of precious metals it senns dificult to envssge & ‘more economic approach on the large scale thin @ more of less autogenous Integrated smelting process. However, special circumstances wil be mt with all lover the world in the extractive metalluray feld. With the advanced level of the ‘modern chemical industry, the possibilities of using low-temperature chemical reactions on the commercial seule in the meta! industry are ineeasing. In the following scctions these possibilities are outlined by examining the fel ‘of hydrometallorey, which deals with teebniquos of producing metals by reactions taking place in liguid aqueous and organic phases 3 Hydromotalturgical processing routes for copper For the treatment of complex ores which are dificult to upgrade by physieal means there will constaatly exist a need for alternative routes. Proosssing by hydrometal- Iurgicaltezhniques will most Hkely be the only way to deal with these materials bbeeause ofthe prohibitive energy requirement for heating up large quantities of worthless materials in smelting proceses, Furthermore there are miny options available in the further treatment of solutions of metal salts. Th this context not ‘only aqueous solutions of the metals should be considered but also the use of ‘organic solutions. This brings us to the modern separation technique of solvent extraction, which has introduced a new dimension into the hytdrometallirical processing of metals, In particular, for extracting copper fons from aqueous leach solutions a numnbor of spoifie selective organic reagents have been developed and ate available from several manufacturers. On the market there are atleast four product series: the LIX reagents from Henkel Corporation; the KELEX reagents from Ashland (Chemical Co; the Shell Metal Extraceant $29 (SME $29); and the Aconga P-50D0 Series from Imperial Chemical Industries Ltd (Acorge Ld), "These extractants ate all chelating agents acting as cation exchanges by rsleas- ing hydrogen ions while selectively extracting eapper ins 2RH + Cute Zt UR, + 2+ (A bar over a substance indicates that itis preseat in the organie phase which comprises the extractant in a diluent, usually a hydrocarbon.) ‘The LIX and the SME series are derivatives built around hydroxy oxime sroups In the Kelex series the chelating property is based upon §-hydony quinoline While the Acorga P-S000 is developed from the parent slieylakdoxime.!™* In addition to being selective for copper, pariclarly in preference to iran, the ‘extraction will take place directly from aeid leach solutions, Using the normal12 Guanar Thorsen solvent extraction techniques for eopper liquors, the acid produced by the extrac- tion reaction shovn above need not be neutralised. The extracting power of the chelating agents with respect tthe acidity level ofthe lech liquor wares and this is reflected in the pH¥ dependence of the equilibrium constants of the extraction However, ifa strongly extracting reagent is used, the extracting power has to be pel for when the revere reaction fakes place, stripping the copper From the organic ‘hase with sulphur ai for recovery by clctrowinning from an aqueous sulphate Solution. Thus for LIX 70 itis reported that at last 300 gil H.SO, i required for ‘rippiag, which would not be suitable fo electrowinaing2 AC this high sulphuric ‘cid concentration, however, the recovery of copper as copper sulphate erstals ‘after stripping fom the organic phase could be an alternative to electcowinning. Fig 3 shows in principle the flowsheet for copper production by leaching, sol+ ‘vent extraction and eleetrowinning. The ial proces consists of three closed-loop eee arse oon 7 stance ie S. Copper production by leaching, solvent extraction and eleccownnlg, Extractive metallurgy of copper 13, circuits where the solvent-extracton loop will bring the copper selectively from a dilute leach solution (1-5 g/l Ca) into the orgaie phase from which it wil sub- sequently be stripped into an aeid sulphate electrolyte ata high conceatration of 30-50 gl Cu, suitable for eletrowdnning. “This kind of procesing i parculrly sted fr reting low-grade oxide ors and sulphide mine wastes where the leaching isa lowest operation such as ‘actrial leaching and heap, dump of inst lesching with sulphuric aid. These leaching operations are dealt with ia the chapter ow uranium extraction in this volume 41 Vat leaching ond agitation leaching of oxidised copper ores ‘Vat leaching has ususlly been eared out in oder to praguoe a pregnant leach solution of sucient copper concentration (30-80 gf Cu) for dretelecrowinning ‘The Jeaching takes place by immersing crushed ore in 50-100 gi sulphuric acid solutions in large rectangular vats. Sequential leaching in a series of vats with a fontinuous flow of leach acié through the vat system is the normal operating practice. ‘With the introduction of the solvent extraction technique there is tend to ‘operate ata much lover copper concentration inthe leach circuit fo optimise the ‘overall production line, Furthermore, the modern plant designs seem also to favour the more eontolable agitation leaching in tanks in seras with the agitation provided by ar (pachuca tanks) or by mechanical means. “This sthe casein te new Anamax oxide plat at Twin Bute, Arizona® which came on stream in 1975. The main copper mineral in the orcbody i ealeopyrite (CuFeS 9, but cap oxidation bas progressed to depths of several handed fet with | copper content save 0:6% Cu, From stockpiled sources witha grade of about 1% recoverable copper, there fs now production at a eapscity of 10000 tons per day of ore. Fg. 6 show the fowshoet of che Anamax copper oxide plant. “After grinding ané milling the oxide ore materia is leached in five mechanically agitated, robberlined leach Yanks, After a total residence time of about § hous ‘oft of the sluble enpper has been sched. Ii intersting to aot that the eos sumption of sulphuric acid (added as 95°27) is up to 250 Ib pe ton of ore. This works out tobe more than seven times the equivalent acid required teach the 1% copper contet. This example Hlustates quite clerly the importance of local conditions and the integrated operation of tw diferent plants, since te reported ‘hat the acid is supplied in tank cars from a nearby smelter. “The pregnant liquor containing bout 25 gl Cu i extracted t9 008 gl Ca ia four stages with LIX GIN. Stripping is carried out in two stages producing an electrolyte soltion f shot $0 gi Cu nd 90 gi 1,80, for eletrowinning. The oppor dtop isthe tankhouse is fom $9 down to 25 gl Cin spent electrolyte, "A similar approach to that at the Anamax oxide plant seems to be contemplated14 Gunnar Thorsen ¥90¢——, £ Lenco |e —— | lsocvent xen Fig. 6. The ANAMAX oxie pan forthe metallurgical treatment of Chingolacupriferous mica ores in Zambia.* The -micaceous ores are found inthe upper levels of most of the sulphide orebodies in the Copperbel. The eupriferous mica mineralogy is quite complex, the copper ecurting as malachite, pseudo-malachite, crysocolla and cuprite, ‘The copper Content usually varies within the range O-5-1°5%, The ore is readily disintegrated ‘Extractive metallurgy of copper 15, toa very five size, with comparatively itl grinding energy, which is of advantage for the leaching step. From a aurber of laboratory tests it has been Found that due to the slow leaching rates at ambient temperature, a hot dite acd leaching at @-70°C will probably be more economic. Furthermore, the use of agitation leaching i favoured because of the control ofthe leaching reaction. The proposed flowshect forthe process is shown in Fig, 7. It should be noted that the solvent extraction technique is included, which in this case plays a very important role due to the signiieant quantities of magnesiin, ron and aluminiat ‘shih wil be dissolved from the mica and whieh make other separation teehniques ficult and expensive, 1 [etn See aoe | i 7 roped estnent oe fo casos or, eis interesting to not th Js sated that the main drawback of the proposed treatment route for the Chingola micaceous ore isthe large quantity of sulphuric acid requied. From the test results it may be sen that about 90" ‘ofthe copper16 Gunnar Thorsen has been leached from the mica sample with an acid consumption of 6 H,SO, per grammie of Cu, Although this is almost four times the quantity required for the ‘equivalence of copper and sulphate, ie the Anamax plant the acid consumption is almost tive as much again per gramme of eopper prodised, ‘Again this is confirmation of the importance of local conditions which are shown in the stated conclusion thatthe required sulphuric acid has to be provided by additions to the smelter gas collection and acid manufacturing facies of the Zamnbion Copperbel 3.2, Hydrometalurgy for copper concentrates ‘Of the copper-bearing minerals chalcopyrite (CuFeS,) is by far the most abundant but represents also the miain challenge in copper hydrometallurgy due to its com paratively. modest reactivity in leaching media. The chemistyy of processing Chaleopyrite Looks attractive, however, in that the prinepal leach reation with sulphuric acid may be represented by: CuFeSy + 1,80, + $0, + CuSO, + {FeO 428° 0) [the extent to which this reaction osburred was satisfactory and the solid products, izon oxide and elemental sulphur, could readily be removed, this would Teave a cupric sulphate solution ready for an electeowinning or hydrogen reduction stage for copper metal, The sulphuric acd would be regenerated and be in balance with the above reaetion for recycling to the leach syste, ‘Several atempts to devie processes along the lines of reaction (1) have been suade® but gencrlly the low yield of this reaction appears to be unacceptable. Tt hasbeen reported that under optinium conditions of a temperature of 115°C and fan oxygen partial pressure of 200-800 psi only 65% of the copper was leached after 2} hours The attraction and advantage of a sulphuric acid Jeach system is quite obvious for leaching sulphide minerals. Further developments have therefore appeared, such es the recent Sherrtt-Continon process which will be discussed below. This willbe followed by a deteription ofthe main routs in ehlocde leach systems where the major part of the activity in hydrometalurgical processing seems to be tnking place at present. In addition, the use of nitric acid as an oxidising agent will be {described and also the Inter developments in the Arbiter proces, where the fotma~ tion of Chevreul’s salt as an intermediate product seem to appear as a common feature with an interesting process making Use of acetonitrile as a strong complex- ing agent for cuprous ions 43. The Shorritt-Comineo process ‘The Canadian companies, Sherite Gordon Mines and Cominco Ltd. have in & ‘Extractive metallurgy of copper 17 joint venture developed 1 process for copper production from sulphide con- entiates“ The main objective of he projet was ~ asin the eas of most projects — te develop a proces applicable 10a wide range of concentrates. eis interesting 19 note that one of the reasons for choosing a sulphuric acid system was the potential recovery of precious metals. According to Sherstt-Cominco, sulphate sytem rather than a chloride route isto be proterced i ths respect The Aw and AB te covery is claimed to be comparable to smteling practice and the Cu recovery is reported 10 be 98% ‘At an early stage in the proosss development it was reais that a serious problem appeared in the form of iron slimes. For this reason a sslectve removal of the bulk of the iron prior to the oxidation leach of the copper values was presrite. This leads to a characteristic and unique feature of the S-C Process: the Selective and complete dissolution of iron a one of the primary processing steps “This is considered as equivalent the converting sage in pyrometallurgcal smelt ing practice for copper concentcates. The analogy may in some respect be justified, in particular on the bass of the subsequent precipitation ofthe iron as jarosite Like the stag-forming ion in pyrometallurgical practice, the precipitated jrosites in hydrometalluray do not seem to have achieved any commercial valu. On the contrary the material must usually be disposed of asa deposit which for environ= rental reasons will tend to inorease both the operating and capital costs 1 seems therefore that methods should be sought which would recover and separate the dissolved ion to make a saleable iron product rater than the jarosite prespitate. On the other hand in the ease of farther oxidation of the elemental Sulphur to sulphate, the sejecion of iron as aroste wil represent an outlet for sulphate. Thus the precipitation of jaroste may be used to contol and Keep ia balance the sulphate level of the processing circuit. simpli block Now diagram ‘of the proces is given in Fig. 8 331. Selective leaching and removal of ron, To achieve the goal of rejeting iron pYior tothe oxidation leach ofthe copper, two pretreatment methods representing Front-end options were developed in the S-C Process. A thermal pretreatment proesduce seem to be the most versatile of these, especially fr treatnent of Io¥~ rade concenttates containing pyrite in the chalcopyrite cancentates. This ie & two-stage process starting With removal of labile sulphur by partial decomposition ofthe sulphide minerals: SCuFeS, > SCuFES,4 + 1S, o TFS, > FesS, + 38, o18 Gunnar Thorsen “This is followed by a reduction step with hydrogen SCuFCSyy + Hy + Cages, + 4FeS + 1S ® “eS + Hy > TFS + HS o Ny204 mayer bir etesenl_POANT l= | ae | pfs ea [1 ruraricaren|—- e305 Fig. 8. The Shecrit-Comiveo copper proces: simplified block Row diarsm, Extractive metallurgy of copper 19 The majority of the iron wil by this treatment be converted to FeS (Wrote) with @ rminor put of the ion in the copper mineral bornite. The activated ealene is then rujected to an aid leach by which the trite is eaily dissolved FeS 4 H,SO4 + FeSO, + HS o leaving the bornite asa leach residue which is highly cessive in the subsequent oridation Fach of the copper CuFeS, + 61,80, + 30, + SC¥S0, + FeSO, 4 48° + 61,0 o The iron dissolved at this stage must be dealt within the further purifeation| prior to elstrowinaing of the copper. It has been reported that the solution purifeation is casi out by 2 high-temperature oxidation hydrolysis sep which emoves iron as hematite (FeO, savenging impurities such as Te, As, Bl, Sb, PO, ‘and Se by coprecipitation with iron oxide, Ite also reported that precipitation of| icon as josie a a lower temperature docs no scavenge impurities adequately. Te may be noted that although the amouat of iran in solution after aching the copper is modes, the concentration is far too high (6-10 gi) for hydroxide pre tipitation. On the other hand it seme thatthe intraductin of a high-emypertare lonidation hydrolysis step for the ion removal must be a complicating and costly ‘operation. As mentioned above, however, the main purpose af this step i purifiea- tion for efsctive rsmoval of trace amounts of impurities don to allowable lvels Which are very srietly enforced, Removal of Se is reported to be particularly dial. Reduetion to Set has been found necessary prior t the coprecipitation ‘vith iron. The reduction step involves heating of the ferrous-contaning leach liquors to 200°C under a noa-oidising atmosphere to reduce the Se" taSe'® by the Fe. This is followed by oxidation and hytrolysis ofthe remaining Fe and the coprecipitation of impurities. Tn addition tothe thermal pre-treatment there isa second front-end option of fan activation Teac teation: CuPeS, + CuSO, + 2CUS + FeSO, © “This replacement reetion is found tobe highly elfetive for hornite concentrates, less efeat on ebaloopyrite while pyrite dass not reat, Although the activation leach reaction above is based upon chaleopyte, the yield ofthis particular reaction may therefore be rather limites. For further treatment of the Boeaitepeodast of ‘equation @), however, an ativation feeh is bound to work with the man reaction Cu,FeS, + CuSO, + 2Cu,S + 2CuS + FeSO, o20 © Gunnar Thorsen Taking both aedvation stops ito account, the Sherrit-Comineo Process offers the possibilty ofa selective leaching and controllable dissolution of iron forming a {errous sulphate solution. By combining the two front-end options it should be possible to optimize the amount of iran left for the purification step ia the subs equent oxidising leach of eapper, Its elsimed thatthe activation step should not be too efficient and that a finite amount of iron should be available for purification. However the level of iron was kept at 1-2 gl one might be inclined to tink in terms of @ puriflestion step similar to that whichis practiced for the neutral Teach solution in the zine industry. Normal practice there is to precipitate about 1 ail Fe ts ferric hydroxide which is highly afetive for seavensing impurities from the neutral zine sulphate solution, 2.32 Irom rejctin, The main pact of the iton which was present in the con entrates appears a8 ferous sulphate solution from the acid leach in which the trolite was dissolved. It has been found that rejection ofthis iron by precipitation of jarosite ata temperature above 60°C isthe best choice, adding ammonia so as, ‘o form ammonium jarosite. Simultaneously, the ammonia will act partly as a neutralising agent forthe acid from the hydrolysis teaction: 6eS0, + INH, + 1405 + SHO ~ 2NHY FeSO) (OF)¢] + 24,80, (10) It is reported that work isin progres to try to separate iron as hematite rather than jeosite. The problems encountered, however, will most likely be connected with the sulphate system itself, t seems generally to be very dificult to produce aa fron oxide product with a sulphur content low enough for it to be aocepted as a saleable produet for iron making, Alternative solutions to this problem, such as folvent extraction of the iron in combination with hydeolysis reactions in the ‘organic phase, which is outlined i the chapter ofthis volume dealing with zinc extraction, should be worth looking at in connection with upgrading the iron to sake a commercial product, 433. The copper winning circuit. One of the min problems in the copper tleoui coms to be the removal of traceelement such 8 Te and Se. The oxidation leach reaction (7) gives a cupric sulphete solution contsining about 100gi! of ‘copper asa basis for depositing capper metal, Shr and resis sulphides are separated by flotation, leaving previous metals inthe final residue in concentrated form. As long as & small amount of copper islet inthe leaching operations, the precious metals and molybdenum will ot be dissolved in the sulphate system. AS ‘ill be sen from Fig. 8 there are two sulphur-contalning gases, coming fom the thermal pretreatment and the acid each and which may be integrated in a Claus plant. Porthermore, a zine removal step has been included, recovering zinc by precipitation with hydrogen sulphide. Extractive metallurgy of copper 21 Ie il be noted that although the $-€ Process in many respectsrepreseatsa pure hnydrometllurgicl process, the lac of solvent extaction steps, a least as optional Mteratives, i striking. The nian setae involved ~ copper, ion, zine, as wll a3 the many impurities present ~ should lend themsves to solvent extraction routes [No doubt solvent extraction techniques have been discussed seiously during the process development. The processing fowshect seems 9 reflect, however, that ‘companies try, a8 far a8 posible, o ws the kinds of process with which they have experience, when introducing new methods of teatment which appear 10 have advantages ‘The S-C Proces, in its present stage of development, is heavily loaded with a reat number of process stops, some of which are very cot, ike the high tom= perature/pressre oxidation hydrolysis operations. No doubt the overall process ray work and is technically feasible but the impression of an uafavourable com- plexity is predominant. The major weakness of the S-C Process scems in several, ‘ways to be connected with the iron problem: fsty, due to the ion rejection as the low, oF negative, value product jarosit, and secondly, on the grounds of eo peating this technique for puriiation purposes in the oxiation leach circuit. ‘Theee seems to be a great challenge to ty to solve the pusiation problem by more direct sean, fr instance by intoducing solvent extraction techniques into the peacesing cicuit, ‘The Sherrit-Cominco staff are to be congratulated foranexeellent presentation lof thee series of papers and for their openmindedness and extefuleonsidevation of the problems encountered. Its intresting to note that, inspite of the complexity of the overall process, a well asthe diiulies met in solving the practical prob: lems, optimism is clearly expressed by the declaration that ‘the S-C Process (is) 4 Vable alternative to the smetnglelectrorefinng route traditional in the eopper industy 34 The Cymer process ‘A msjor attraction ofthe chloride processes for primary copper production is the possibility of @ dict leach operation on the copper minerals at atmospheric pressure. A number of processes starting from this prineiple have therefore been eveloped or are presently in progress.2*#? "A unique approach is demonstrated in the Cymet Proces, studied extensively at the pilot plat stage by Cyprus Metallurgical Processes Corporation. The fundamental concept of the Cymet Process is based upon an electrochemical sireuit where the sulphide part of the mineral is oxidised to sulphur at an anode with the dissolution of metal ions, and the reduction of thee fons to metal at @ cathode, Figure 9 presents the fowsheet of the prooess tested for chalcopyrite at the Cymet plant. Both copper and iron aro recovered eletrfytially as metal pro- ducts while the oxidising agent FeCl, is regenerated simultancously in the same22 Gunnar Thorsen aaa [ TEARS (Seon {—ETECTRO= | corse poduet olssoLuTON ero SEER | sulnur [acento | | na | — ae = aie a | [Rae ne Wrongs [He ton ones ‘sonend cells, Although the we of eictvical energy is kept to minimum by the arrange tent ofthe elestrochemical circuit, t appears that the economy ofthe process will be highly dependent on the market price which may be obtained for the iron metal product, Is elsimes that a high copper yield of 987% may be achieved, but it has so tobe noted thatthe copper is precipitated asa powder inthe chloride soliton fand has to go further to an eleteorefising step, shih will add to the capital and ‘operating costs of the process ‘Extractive metallurgy of copper 23 ‘The basic chemistry of the main teps may be represented as follows: “The leach rexetion: GFeCl, + 2CUFES, + 2CuCI + BFeCI, + 48" ay “The dissolution takes place i the daphragm-fited electrolytic el, the equations being given as: (CuFeS, 4 SHCI ~ 30+ CuCl 4 FeCy 428° 4 38+ 2) 3CuCI + 3e = Seu" + 3c ay B+ 4 3c SHI as ‘The spent catholyte soltion is further depleted of copper by cementation with metalic ion, fllowed by a sill further purication step by zine comenttion 10 remove trace cements sch as Pb, Sb, Bi and As, The dissolved zine from thie ‘operation is subsequently recovered by solvent extraction with atetary amine. ‘The purified ferrous chloride solution is subjected to electrolysis, making high purity fom eathodes while ferric ehlovide is regenerates atthe anode SFeCl, + 6e + 3Fe* + 6C- as GFeCl, — 6e + 6 ~ OFC, a9 ‘The imbalance between cathode and anode efcences resus in an excess of dis Solved ion which it ejected from the processing circuit by hydrolssis and pee cipitation of iton oxides. ‘The major problems encountered during the process development are most likely connected with the operation of the eletrlytic cals, coupled with a poor quality ofthe capper power which will have to wndergo ferther refining. A sa factory price level for the large amounts of electrolytic ron product would probably be very difclt to achieve for the comparatively large quantities which would be produced ‘Apparently, the Cymet process has not been sucessful its base version. An improvement, or rather a new process, has therefore beea anounced receaty®” asthe Cyprus process, while atthe same time it was delared that “Cymet s dead’ 35 The Cypmas process Having leent the hard way by experience during the Cymet process development, the new ehloride process is based on a eireit consisting of more technically con-24 Gunnar Thorsen ‘ventional steps, The overall flow sheet for processing & pure copper concentrate such os chalcopyrite fs shown ia Fig. 10 Lesa [ee | eo —ete onmgggr [Htc 2 fone see a raoxe mate PGI | resect ‘10. iow shes forte Gor coger pecs. ‘The concentrate is leached in a two-stage proces using a mixed solution of| ferric chore and copper chloride for leating. In the first stage the copper ions in te intial leach solution ee inthe euprie state and both the Ferrie and the euptie fons act as oxidising agents in the leaching process. The basic reactions involved inthe frst leach stage are: AEC + CuPES, — SFeCl, + CuCl, + 25° an 3CuCly + CUFES, + ACCT + FeCl, + 25° as) CUCL, + 8° 4 44,0 + 6CUCI + H,S0, + GHC 9) Daring the dissolution proses, the lech ¢olation will become highly con- centsied in cuprous chloride and after being beld in s standard thickener for Slidliquid separation the overflow solution is passed to. erytallser where ‘cuprous chloride fs precipitated in a single stage vacuum cooler After dying, the tuprous chloride fe along with sand particles into a fui bed restor for hydro- gen reduction, thereby producing copper meta: CuCl + HH, + Cu + HCI) 0) Extractive metallurgy of copper 25 The copper forms around the sand particles and grovs in size forming nodules, ‘The copper nodules and sand mixture will be further melted in 8 conventional farnace, The melting step will Include slggiag to zetur the sand tothe reactor. “The mother liquor (rom the erystallser goes to hydrolyse step or iron which is controlled by the oxygen supply and where the following reaction take place ACUCI + Og + AHCI -+ 4CuCl, + 24,0 en APECI, 4 Oy + AHCI AFSC, + 281,0 ea FECL, + 2Na,S0, 4 OHO + NafFeySO)fOH)e] + INKCI4 6HCL 3) eC, + 6H,O + F(OH,(H,0) + 3HC1 oy ‘The hydrogen chloride supply for reactions (21) and (22) will be in balance with, the HCI recovery from the hydrogen reduction step, equation 20), and the acid liberated by the hydrolysis reations (23) and (24). The product of the iron pre= ‘ipitation is made up of jrosites and hyerated iron oxides, and the oxidants from this oxy-hydrolysis step form a slrey which is passed to the second stage leach, “This is esentilly a ferric chloride feach and ia this stage the remainder of the copper is extracted from the concentrate and converted to cupric eloride. Aer passing through a thickener the liquar product is returned tothe fis stage leach and the underflow slay is seat to the tls filter and then t the tilings pond 45.1 Recovery of by-producte and iron rejection. The Cyprus Procest looks attactve on the flowshest and has the simplicity of approach which is a goad Starting point. However, the dseussion of the process 50 fac has been limited to the treatment ofthe pure copper concentrate. I has been sated that by-product recovery is posible and that this has been demonstrated in the laboratory for the recovery of silver, gold, molybdenum and sulphur. When products are to be re- covered from the residues thas to be noted that the tile will contain the appesi- able amount of iron precipitated as jaosites and hydrated iron oxides (gacthie) ‘Very ite has been mentioned about the ioa rejection apart from te hydrolysis rections (23) and (24). Its belioved that the practical operation ofthe step for pre cipitation of jarostes and goethite i ikely to represent, at ver least nuisance i the process circuit. On the other and it will to a certain extent probably have the audvantage of ccavenging some of the impurities prevent. ‘As an advantage claimed for the process, it hasbeen stated that its operation produces no pollutants in the ai or water. Tis is obviously achieved, however, by Including liquid tight areas for impoundment of tailing produets. With the large ‘amounts of iron precipitates iavolved this i likely to add a heavy burden to the26 Gunnar Thorsen pital and operating costs of the process. Nevertheless, its stated?® that taking ‘those precautions into account, a feasibility study forthe Cyprus process shows that plant can be built and operated ata lower cost than eny knowa competing process, 56 The CLEAR process Duval Corporation seems to be among the leading companies, if not the leading fone, in the application of chloride system for hydrometalluegial processing of copper concentrates. A.32 500 tone per year plant for commercial operation has been buile in Arizona and further extensions are believed to be under con- “Apaet from the patents not much detailed information has been given about the CLEAR process. The essential feature i however, that it recovers metallic copper from shaleopyrite nd other eopper-contaning materials by a eri chloride ‘uidation leach, The resulting roltion of cupric ehlorde is reduced to cuprous {hlorde from which copper i ecovered by electrolysis ina dlaphragm cell eer “The flowshect of the process, aevording to the patent, is shown in Fig. 11. As in the Cyprus process, there are two stages of leaching. What is called the ist, ope, described as the ‘oxidation’ stage, i essentially based on the reaction AF eCl, + CaFeS, ~ SFeCl, + CuCl, + 25° e9 Extractive metallurgy of copper = 27 hich i identical with the fst ofthe reactions in the Cyprus process. The resulting cupri ehloride solution is passed on to the second leaching sage, the “redaction” stage, whese the main purpose i to reduce the cupric fons tothe euprous state, by further reaction with the copper bearing material BCCI, + CUES, + ACuCI-+ FeCl, + 25° 25) Peters has discussed the CLEAR process on the basis of the patent die closure and suggested thatthe existing plant probably does not use exclusively chalcopyrite concentrates for the reduction stag, but might ule more sronely reducing substances, such as eement eopper, OF part ofthis sep. This feature is ho contemplated in the patent where iis sated that the reduction is preferably accomplished jn two steps; fist, reacting the cupric chloride solution ith fresh copper sulphide ores ata contcolied temperature, and then with additional reducing ‘gent, such as materials containing metallic copper Cu" + CuCl, + 2cuCt @ ‘To keep the cuprous chloride from precipitating, a suitable amount of sodium Chloride is inctuded in the process solution to form the CuCl anion. The solution iseleciolysed in a diaphragm coll where hall the coppers deposited atthe cathode And the other haf is oxidised to cupric chloride. Thus the ideal material balance wil be ereated when half of the copper-bearing material is leached in the “oxida tion’ stage (Cettion 25) and the other half in the “eduction” stage (reactions 26 and 27 combined) It is to be noted tha by this ideal balance the electrowinning isa low energy step because the anode oxidises CuCl 9 CuCl, while the cathode reduces CuCl to etal ata reversible eel potential of only about 0-4 vols. In practice @ somewhat higher potential is necessary to drive the electrodepostion, Peters has pointed fut the fact that even with 2 poteatial higher by 1 vol, this represents lee than fone quarter of the energy involved in ordinary eletrowinning from copper sulphate solutions. “he copper metal product from the chloride solution electrolysis is most likely tobe further refined for making a wire bar quality. It is to be noted that any silver present inthe ores reported co be solublsed as silver chloride froma which metallic silver can readily be reeovered, Regeneration and rejection of iron. The regeneration of the fre each accomplished by oxidation of the rafinate solution feo the electolssis ‘sth either sir or oxygen, The presence of cuprie chloride catalyses the oxidation ‘of ferrous to Feri ehloride.28 Gunnar Thorsen “The necessary’ bleed of ito from the proses cick not revealed in dis Foam the patent dilosue ht sesms, however, that once again the approach of Prccipiign of res and taste rn ene by hyo feorported eaton of meal ne imouah the advantageous scavenging elects of core purty scereds the same epost problems wil be metas in the Cypres provers 37 The Minmet Recherche process 1X very interesting, approach sing @ cupric ebloride solution as the Teaching edit, and recovering the copper by solvent extraction ~eleetrowinning has been ugeeited by Minimet Recherche (lmetal Group).* By combining the solvent ex- faction sep and the regeneration of the leach solution, using oxygen as an oxiis- ing agent, only electricity and sir are required to operate the prooess — | ——Lssasgave » 17 | Ll ii ah tl-ois ae I Fig. 12. The Minlmet Recherche proses for copper (PM—Preciows Metals) Extractive metallurgy of copper = 29 ‘The basic Nowshet is showa in ig. 12. The leaching sep is carried out with a ‘aprie chloride soltion containing about 250 gf of sodium chloride to avold pre i Lgrpretex woo, amon’ ot Sos \ Lfeosrapene }—[h STEREO y fea See cfSithne RIE eee co RESTEONG | Sen iv ‘The extractive metallurgy of deep-sea manganese nodules 49 diluent, Five miner-setlers are uted for extraction and the pH is maintained st 2 in each stage by additions of NAOH. Copper is stripped from the loaded organic in ive stages with sulphate electrolyte returned fram the copper electrowinning step, which has « hydrogen ion concentration of atleast 3, In one patent, copper Is extracted with a organie station containing 10 volume % Kelex 100 instead of LIX GEN". In this case, only 4 stages of extraction and 3 stages of stipping are sed 243 Nickel and cobalt removal. The rafinate from the copper removal step ‘contains nickel, cobalt and manganese inthe chloride or sulphate liquor. The pH ofthis liquor is adjusted to approximately 4-5 with 2N sodium hydeoxide solution and then the nickel and cobalt ae extracted together inta an organic phase con taining 10 volume % Kelex 100 and 20 volume % iodeeanol in Kerosene OF [Napoleum. Five stages of extraction are used and the pH is maintained at the esired value by additions of NaOH. Nickel is then selectively stripped from the loaded organic phase, which con- {tins nickel and cobale, by contact in three stages with sm aqueous solution 3N in hhydrogen fons. This solution is return electrolye from the nickel electrowinniag ep with added acid to increase the hydrogen ion concentration to the desced value. Iti interesting fo note that nickel electrowinning is done using @ nickel chloride electrolyte when the liquor fom nodule leaching is chloride based! #281 snd from a nickel sulphate electrolyte when the lech liquor is sulphate bazed.* After nickel stripping, cobalt i stripped from the organic phase by contact in 4 stages with 20 weight % HCI solution. This produces an acidic cobalt chloride Solution which is unsuitable for cobalt electrowinning and, in order to conserve the strong HCI solution for rease in stripping, cabalt is re-extracted into a 10 volume % solution of trsisooetylamine in Kerosene or Napoleum, This extractor ‘carried out in thre mixer-stlers. Stepping is carried ou, als in three staze, with lectrolyte returned from the cobalt eletrowinning step. Tn one patent, a 10 volume % solution of LIX 64N is used in place of Kelex for the co-extacton of nickel and cobalt! In this case, aly 3 stages ofextrastion are used but, apart from this, the process is identical to that deserited above. ‘The final aqueous rafnates from the solvent extraction proseses are basicaly solutions of manganese chloride or manganese sulphate. These ace sully further purified by precipitation of heavy meal impurities as sulphides, by the addition of Inydrogen sulphide or ammonium sulphide"° resulting in substantially pure ‘solutions of manganese chloride or seiphats ‘Two alternative methods of producing manganese chloride solutions from Pregnant chloride leh liquors are described in other patents. In both ates, oa, Dovpo Ventures saved exactonDowahct Adapicd fm OS ates 3805 2H)50 A.J. Monhemius is frt removed from the leach liquors by amine extraction and then the remaining mnetals are removed together feom solution by precipitation. This is accomplished cither by cementation with manganese metal® or by the use of H,S to produce & bulk precipitate of metal sulphides. These precipitates will of course require further processing. The methods used are not revealed, but are likey to favolve redissoltion, followed by solvent extraction for metals separation. 22. Manganese recovery The recovery of manganese metal fom manganese sulphate solutions can be accomplished by aqueous eleetrowinning*#® However, a problem arises in the Aisposal of the sulphuric acid generated in the eleetrowinning step. A partial ‘olution to this problem i revealed in a patent which will be discussed in a Tater ‘The recovery of manganese from manganese chloride liquors requires novel technology and a number of posible solutions have been developed by Deepsea ‘Ventures: recovery of manganese metal by either reduction with aluminium metal or subhalide, of fused-salt electrolysis, oF recovery of manganese as an oxide by pyrobydrolyss of MnCl, 2.2.1 Reduction with alumni. The operation of an aluminium reduction cel js outlined in US Pat 3 §32 165! MaCl, 4H,0 js erystalised from the aqueous Tiquor and dred. The exstals are added toa pool of molten chlorides contained in ‘refactored reaction vessel The pool contains about 50% manganese chloride fd the balance is alkali and alkaline earth chlorides. There i a vertical tempera ture gradient within the pool, with the top at 1150°C and the bottom at 1300°C. ‘A substantially stoichiometric amount of serap aluminium turnings is added together with the manganese chloride. Molten manganese metal is tapped from the ‘bottom of the reaction vessel and aluminium chloride vapour is removed overhead through a vapour outlet. “The aluminium ehlovide vapour is pascod through a tower containing the i> ‘coming slominium scrap to preheat it and to recover any manganese chloride carried over, The tier is maintained at a temperature above the boiling point of aluminium chloride "The sluminium chloride vapour is then passed into a reactor where it i com {acted with water vapour at approximately 400°C. Aluminium oxide i formed and recovered as by-product and HClis collected and recycled teaching 2.22 Fused salt electrolyts. An alternative method of producing molten man- ‘eanese metal, which does not require 8 supply of Scrap aluminium, is fased salt tlectrolysis® Manganese halide is reduced in an clctrlyss eel! containing a Iolien mixture of halides. One component of the mixture the halide ofa reactant ‘The extractive metallurgy of deep-sea manganese nodules ST etal, prferably magnesium of sluminius. The elactrodes in the cll are inert and the voltage drop isnot sufcient to cathodiclly reduce the manganese halide tro manganese metal. The proces i believed to operate by reduction of the reactant metal halide tothe elemental state. The reactant mal then reats with the mane fanese halide to give manganese metal and to reform the reactant metal halide ‘Thus ther is substantially no net loss ofthe reactant mal from the el, Elemental halogen is formed an removed at the anode, ‘The rector used is in two parts, with the upper postion being the electrolytic cll containing the electrodes, The enrent Row ie horizontal, The lower portion isa molten manganese colletion section. The molten halide bath in the ell section ‘mixture of at east one alkali alide, at last one alkaline earth halide, the reactant seul halide and manganese halide, The alkali and alkaline earth halides that are {quoted as useful sre the chlorides, bromides and iodides of Na, K, Cs, Rb, Li, Cy Ba, Se and Mg. The halide misture contains about 10 to 25 we % reatant metal halide and up to 10 wt % manganese halide. Ia order to malataia the molten reactant metas dispersed droplets in the halide mixture and thus to masimice the surface ares for reaction with the manganese halide, an antagglomerting agent such as B,0,, Na,B,0, or KO, s present in the mixture at concentration of 10-*to 10-* we 7 The manganete is eollete inthe molten sate the ower part fof the reactor, whichis maintained at temperature of 1260-1300°C. In order to prevent loss of halides by volaiistion, there is @ temperature gradient in the eacor and the top susfae ofthe halide bath ie ken in the range 800-1000°C, 223 Pyrohydrolyis, The production of manganese oxide rather than man- fganese metal is described in another paten.#® The hydrated manganous chloride, MnCl_Hi,0, which is eeystlised from the purifid chloride leach liquors, i frst dried to the sahydrous salt. This is passed toa pyroydrolysis reactor where it is reacted with steam at SSO°C to form manganese oxide and HCl, which can be reoycled, Manganese oxides can be converte to manganese metal by reaction with the subshaldes of one of the so-called transport metals, which comprise aluminium, slicon or ttaium, according to US Pat 3980 162 % The proces, whichis largely conceptual in design, consists of three reactors in closed eit, Manganese oxide is charged toa reduction reactor where iti reacted with aluminium monohalide~ 3Ma0 + 3AICI-+ 3Mn + ALO, + AICI, o ‘The reation is carried out at about 1380°C in the presence of calcium Muoride, hich acts asa ux for the metal oxides. Molten manganese metals tapped from. the reduction reactor. Aluminium oxide, together with the Nux, is removed a5 a sag and passed to a catbothermie smelter, Here the aluminium onide is reduced52 A.J. Monhemius carbon at about 210°C. Silicon is peesant, go that a molten aluminiamrich slicom allo is formed. This prevents the formation of aluminium carbide ALLO, + 3C + (Si) + 2A1(8}) + 360 ° “The molten soy ie then pass to the subshalide resctor, where iti reacted at bout 1150°C with the aluminium techloride, tured from the reduction reactor, to reform aluminium monochloride ANGI + AICI, ~ 3AICI + (8) “ Similar principles can be used to reduce manganese chloride with aluminiuen monochloride to form manganese ml 23° Frontend processes A large proportion of DSV patents are concerned with alternatives forthe Front fend operations; je. the pretreatment and leaching of raw manganese nodules. As the objective isto disolve manganes, i ie necessary to reduce manganese fron the tetrvalent to the divalent state and this is done ether prioe to oF during the Teaching operations, Both chlorie-based and sulphate-based routes have been Snvestigaed and itis convenient to dicuss them on this basis. 23.1 Chlordecbased procestes. The most ites method of producinga chloride liquor is dissolution of the nodules in concentrated hyérochlovie ack. The acid i suficiently reducing to reduce manganese to the soluble divalent state. The oxida- ‘ion product of the rection is elemental ehloine MnO, + 4HCI+ MnCl; + Cly + 21,0 o Dikect leaching of manganese nodules in hydrochlovie acid Is quoted in a least, four DSV patents. The nodules are ground to ~500 4m and then contacted countercurrently with LI HCL at LOO*C in a fivestage leaching systern The pret ‘nant liquor isa minture of MnCly, FeCl, CoCl, NiClg nd CuCl, with «pH of | t0 22888. A modification ofthis process involves sand-simes spi ofthe ground nodules in a hydroclasifer prior to leaching. The slimes are treated in a thre Stage leaching system vith countercurrent flow of aa 11st HCI soltion. This solution is then contactodcouater-curtenlly withthe sands fraction ina fve-stage system. Additional HCI gos is added during the sands leaching.® “The great advantage of direct hydrochloric avis leaching is that the nodes, which contain about 30% moisture, da not have to be dried prior t leaching, However, as shown in the equation above, approximately half the hydrochloric ‘The extractive metallurgy of deep-sea manganese nodules $3 acid is oxidised to chlorine during leching. This ehlorine must either be sold as & by-product or reconverted to HCI by reeetion with hydrogen, Also most of the iron present in the nodules reports inthe leach solution. An akernative way of ‘sing HCI involves chloridisation at temperatures around SOO°C with gaseous HICLY An advantage of this procedure is that by pasting water vapour over the hot ore after chlordisation, ion ean be converted to insoluble FeO, and is thus sliminated from the subsequent leach liquor, produced by dissolving the eloriised fore in dilute acid at pt 2 ‘The dissolution of ion ean also be prevented by chlordising the nodules in a molten ehlorie salt bath" The nodules are ground to 710m, dried and mixed with a 48% NaCl, 527% MgCl, mixture. This is heated to 200°C for one hour and then to 600°C to forma liquid mass and held for six hours, The percentage conversion of the various metal 19 the chloride form ie as follows: Mn ~ 35-5, Fe~00, Ni~ 76-5, Cu 92-3, Co = 125. The metal chlorides are recovered from the molten lorie bath by raising the temperature to L000°C to volatile ther “They are then carried out ofthe reactor in a steam of nitrogen gas and condensed in water. The extraction of Ma by this procedure can be improved to over 80% by preeducing the nodules wth earbon monoxide at 600°C, prior to ehlordisation. The selective cloridisation of Mn, Ni,Co and Cu can be carried out at lower temperatutes by using solid aluminium of ferric chlorides. Again pre-reduction, ith carbon for example, improves the extraction of manganese. The preseduced nodules are mixed with aniydrous AICI, and heated at 140°C for 2 hrs. After cooling, the mistue is leached with dilute acid at pH 2, to give metal extractions of better then 95% 23.2 Sulphate-baced process. Sulphate leach liquors may be produced by using SO, 28a reducing agent. Manganese can be selectively converted to MnSO, by reacting nodules ground to ~149 umn with SO, in the absence of oxygen in & ‘uidised bed reactor. The reaction is exothermic andthe temperatute rises to about 100°C during the reaction’ Leaching the reacted ore with water counter-curtently in thre stages produces a substantially pure solution of manganese sulphate fram ‘which manganese metal can be won by aqueous electrolysis, Ni, Co and Cu can bbe entracted ftom the solid residue by surrying i in water and passing in air con ttining 10% S0g. Under these conditions Ni, Co, Cu and any remaining Mn dissolve as sulphates, while ison remains insoluble, Alternatively, the selective sulphation of manganese is eliminated and the raw nodules are reacted iectly With an SO,/O, mixture to form the sulphates of Ma, Ni, Co and Cy, which ean be water lesched* An interesting vacation, involving the use of sulphidie iron ores as reducing ‘and sulphating agents, is revealed in US Pat 3809 624: A light excess of sul Phidie iron ore is ssixed with the nodules and the two are ground together to 149S$ ALS. Monhemius 110 um. They are then roasted in aa excess of ai at 400-G00°C to form iva oxide and metal sulphates. Leaching the hot ore with dilute acid at pF 2 results in a soluion containing the sulphates of Ma, Ni, Co and Co. “The aqueous elsiolyis of manganese sulphate solutions produces a spent lectrolyte which is basically eilete sulphuric acid. This eannot be reeyted in the ove sulpatecbased processes and presents a disposal problem. An alternative fppeoach, in which atleast part of this sulphuric acid is reycledy is described in US Pat 39234615!" Raw nodules are ground to ~297 um and leached with ce- cycled spent electrolyte containing 4 we% H,SO,. Leaching i cartied out for ubout TH hours at 60°C, during which time most of the nickel and copper disotves. Ferrous sulphate then added tothe leach Liquor ané leaching i continued for 3 further 6 hours, The ferrous sulphate acs as a reducing agent and soubiies the ‘mangavese and cobalt. Ferous fon is onde to ferric oxide which reports in the fesidue, Airis bubbled through the solution during the final hour of leaching to ensure the foal oxidation of iron. Metal extractions obtained by this process were Min, 91% Ni 84%, Co, 877% and Cu, 81% 3 Kemecot Copper Corporation processes The distinguishing feature ofall Kenneeotts work i that leaching is carried out in ammoniacal solutions, the objective being to recover Ni, Cu, Co and Mo in Solution an to eject Mn and Fein the solid leach residues. The key unit operation ‘Of the various Kennecott procests isthe solveat extraction separation of copper “and nickel fom the aramonincal leach liquors. This is the subject of a number of. plents and has boon desribed in several papers “The orignal solvent exttaction scheme involved selective, sequentia extraction of copper followed by nicks, using LIX 64N asthe extractant for both metals *#¢ ‘One of the main problems in usiag LIX G4N with ammoniacal aqueous solutions is that extraction of ammonia into the organic phase occurs. This has tobe re- moved before the metals are scipped with sulphuric acid, otherwise ammoniuat Shphatebuilés up inthe strippiaglcletrowinning cous. Because ofthe necessity to include ammonia scrubbing tage in both the copper and the ck eres, & toval of 26 stages were requited forthe elective extaction fowsheet. Detaled analysis of thie Nowshet indicated that it could be considerably simplified by ‘opting co-xtraction of Ni and Cu, followed by selective stripping and thi Aosishest option hasbeen the subject of subsequent papers from Kennecott. “The lowshect ofthe co-exteaction/selestive stripping prooes is shown in Fig. 2. ‘The comporiton ofthe feed liquor is Ni, 6-2; Cu, :7; Co, 02; NH, 90; COy S55 glk The extractant is 40% LIX 64N in kerosene and all extraction and striping steps are carried out in minerals at a temperature of 40°C. Co-etration of [Niand Cu into the organic phase requires 3 stages. Better than 99:9 %exirstion of both metals is achieves. About $% of the ammonia is also extracted and the The extractive metallurgy of deep-sea manganese nodules = 55. r = 71 t I aon see | ihe ‘ye soon syte a | eo ion F.2 Kens set extasion wat loaded organic phase contains 25 gl Ny This Tower t9 005 gt NH in the two ammonia serubbing sections, Inthe primary serub section, ammonia is removed from the organie phase by contact in two stages with an ammonium bicerbonate solution containing 17 gl NHy. Ammonia is recovered from the aqueous scrub rafinate. Final traccs of ammonia are removed in the secondary$6 A.J. Monhemius scrub section, by contact in two stages with an ammonium sulphate solution con- taining 27 git Ni. The concentration ofthis aqueous scrub liquor is maintained by a bleed to waste, Nickel is then selectively stripped from the ammonia-free frganic by contact with retura electrolyte from the nickel electrowining section, ‘The return electrolyte contains H,SOy, 40; Ni, 30; Na,8Oq, 100; HBO 18 a “The advance electrolyte fem nickel stripping contains 75 ai Ni ak pH3. The Ni/Cu ratio ofthis solution is 25000/ and itis sitable as Teed to nickel cletrowining ‘oithout further teatment, The transfer of nickel from the organic tothe aqueous phase is slow process reuiring about 25 minutes contact time. Inte plot plant, {his necessitated the use of st stage for nickel stripping to achieve the neessary omtaet time, but the proposed commercial design involves only thes stages, (Shore each stage consists of two miners in series feeding a single ster." The “rganie phase leaving nickel stripping contains 38 gl Ca and 0-4 gil Ni Copper, togetber withthe remaining nickel, i removed in the copper stripping section by ‘contact in two stages with etur electrolyte from copper eleetrowining, The return ‘Sevtralyte contains 160 gil H,S0, and 35 a Co and the copper content js in treated to 45 gin the copper stripping Section, Nickel, whieh alo transfers into the copper electrolyte, does not alfeet copper electrowinning provided its com: Catation ts kept below 20 gl. Theis accomplished by a bleed from the copper ankhouse, The stripped organic, which contains aboot O'S gil Ca, is eesyced to “The development and optimisation of this flowsheet was considerably ex palit by the use ofa computer model developed by Kennecott The extraction Ejotem is chemically complex as there is compatiion between the metals and fmmmonia for the oxime reagent, anumine complexing in the aqueous phase and fpparetly the possibility of the extraction of a nickel ammine complex, ‘The development of a successful computer mode! for such a complicated system was & tonsiderable achievement, It was found t0 be particularly wseful for this sytem ‘because the extraction of nicks! by LIX G4N is sharply desreased by increases in the aqueous snmonia concentration, On the other hand, lashing is improved by increases in ammonia concentration, Computer studies using the model enables thove to confictng elects 1o be optimise Ta'none of the published descriptions ofthis proses, isthe extraction ofcabalt ino the organi phase mentioned. We can assume, therefore, that cobalt in the feed figuor isin the cobatie state singe cabaltic ammine complexes are not ex tractable by LIX 64N, Cobalt in the eobslious state i extracted by LIX 64N. end inthe organic phase it inmediatelyoxidises and becomes diet to stip. Kenne~ ott hold two patents on the steipping of eabalt from LIX solutions, One method involves the ute ofa solution containing 2M FICI and 150-200 fl NaCl. An ‘aqueous to organi ratio of about 2to {is used and the solutions are mixed for 530-60 minutes at $0-60°C." Under these conditions about 907% of the cobalt is ‘The extractive metallurgy of deep-sea manganese nodules 57. emoved and the foss in metal loading capacity of the organic phase is held to 239% In a later patent, mixture of concentrated sulphuric acid with glacial acetic aci, methanol or other lower alcohols are cited. The cid stripping mixture issolves the cobalt-contsning oxime, eaving the Kerosene or other dient as 8 separate phase, On entering the acidic mixture, the oxime releases the cobalt and eee | fees ae | ee ms Fy | Four iiau0]580 A.J. Monhemius the oxime f recovered hy adding water tothe ace mixture to reduce its solubility, ‘whereupon the oxime redissolvs in the diluent phase. Some degradation of the ‘oxime oocurs and the mst loading capacity i reduced by about 25% ‘Although the co-extraction/eleetive stripping flowshest described ahove appears to be the prefered option, an alternative solvent extraction process {nvolving selective, sequential extraction of copper and nickel is revealed in two patents #32 The objective of this process i 1 recover nickel, as metal ot oxide, IWithout having to use electrolytic methods. This is accomplished by stripping opperce,nikel-foaded LIX GAN with @ concentrated ammoniaeal ammonium tathonate soltion, Resioval of ammonia from the aqueous strip Tiquor precipitates, basie nickel earbonate, A slurry of the basic nikel carbonate can be hydrozea pressure reduced to produce nickel metal powder. Alternatively the base carbonate {an be ealened to produce nickel oxide. This can be marketed as such, or rodveed ‘thigh temperatures to niekel metal powder, The solvent extraction flowsheet for this process shown in Fi. 3. ‘Kennecott have not published deteil of the leaching process to be wsed to produce the ammoniacal feed solutions for their solvent extraction processes “However the patent itratare indicates thatthe preferred process is diect leaching ‘of ground raw nodules using ammoniacal armonium carbonate solutions eon~ taining caprous ions. The euprous fons, which are stabilised in solution by amimine fomplexing, act as reducing agent and reduce manganese dioxide inthe nodules, feleasing Ni Cu, Co and Mo into solution, while the manganous fons precipitate asinsoluble manganous carbonate. The cupeous ions are continuously regenerated ring leehing by intcoducing earbon monoxide into the leaching reactor.** “The rections which oovur ae sa tobe MnO, + 2Cu(NH),* + 4NH, + CO, + H,0-+ Maco, + 2Cu(NH,)+ + 20H o 2CuNTT), + CO + 20H" + 2CUNH),* + ANH +O, +H,O “The net overall eaction In eduction isthe su of equations (6) and (1) Ma0, + CO MnCo, ® Im the absence of capper in saution, reaction (8) does not secur and thus copper ean be considered ne acting a6 2 catalyst forthe reduction of manganese dioxide by carbon monoxide 'A deseription of flowsheet for atmosphere pressure leaching is sven in US et 3983 017 and is shown in simplified form ia Fig 4. Raw nodules are ground ‘The extractive metallurgy of deep-sea manganese nodules = $9 ‘ait, > PEBBLE | “ | i =. |) gn 4 Keanecotcuprovs leaching ross. Ada rom US Patent 3983017, to ~3260 jm ina cage mill and fed to a mixing tank where they are slurred with pregnant liquor reeyele and clarified lech liquor. The slurry is passed through a hydrooyclone, where oversized nodule panicles are removed, reduced in size in f pebble mill and returned to the mixing tank. The hydrocyclone overflow, together with part of the clarified leach liquor is fed to the fest of the impeller agitated leaching tanks. Covcurreat leaching at ambient temperature and pressure and about $9 solids, is earred out ina series of from three to sx tanks. The com- positon of the leach liquor is specified in the patent to be within the following broad limits: about 60-140 gi! NH, about 20-60 gil CO, about 2-20 g/l or more copper, about 8-20 gi Ni, about 0:54 g/l Co and about 10-20 g/1 CL. The chloride aries presumably from the sea water contained in the raw, undried nodules. The© = A.J, Monhemius ocesryeyprou on oncenatin inthe ach Iquorf maintained by the ito

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