Atmosphericleachingofenargiteinacidiciron sulphatemediainthepresenceofactivatedcarbon

ImanGhanadandDavidDixon TheUniversityofBritishColumbia,Canada

ABSTRACT
A new method for treating enargiterich copper concentrates through atmospheric ferric leaching catalysedbyactivatedcarbonispresentedinthisstudy.Enargiteconcentratesfromthreedifferent minesinChileandPeruandoneenargitemineralsamplefromtheUnitedStateswereusedinthe leaching experiments under the Galvanox process conditions. Batch leaching tests were conducted in sealed and jacketed glass stirredtank reactors. The results showed that enargite leachingwasuptosixtimesfasterinthepresenceofactivatedcarbon,makingitpossibletoachieve virtuallycompletecopperextractioninlessthan24hours.Thelaboratoryscaletestsindicatedthat desirableleachingkineticscouldbemaintainedafterrecyclingactivatedcarbonparticlesuptothree timestonewleachingtestsandalsoafterreducingthecarbon:enargiteconcentrateratioto0.25.The activatedcarbonlosswasreducedto5%oftheinitialcarbonmassbydecreasingthestirrerspeed whiletheleachingperformanceremainedsimilar.Theeffectsofconcentrateregrindingandinitial totalamountofirononcopperextractionwerestudiedaswell.Thepresentedmethodpromisesa commerciallyattractiveroutetotreatarseniccontainingcopperconcentrates.

INTRODUCTION
Copper smelters are traditionally used to treat copper sulphide concentrates. In modern smelters the conventional problem of sulphur dioxide emission has been addressed effectively; however pyrometallurgicaltreatmentofcopperconcentratescontainingelevatedlevelsofarsenicisdifficult and costly. Therefore, arseniccontaining minerals are considered to be highly problematic for smelters [1,2]. On the other hand, the depletion of clean copper deposits and the increasing demandforcopperemphasisetheneedtotreatcopperarsenicsulphidessuchasenargite(Cu3AsS4) andtennantite(Cu12As4S13)throughviableroutes.Hydrometallurgicaltreatmentofenargitewhich iswidelydistributedinChileancopperoresprovidesasimplermethodfortreatingarsenicbyco precipitating it with iron in the form of scorodite. The overall enargite leaching reaction occurs accordingtothefollowingequation:

4Cu3 AsS 4 + 9O2 + 12 H 2 SO4 12CuSO4 + 4 H 3 AsO3 + 6 H 2 O + 16S

(1)

Themajorchallengeinthisrouteistheslowleachingrate.Catalystsincludingsilver[3],pyrite[4] and activated carbon have been proposed by researchers to enhance the leaching of copper sulphides. Previous studies have investigated the use of activated carbon in bioleaching [5,6], sulphuricacidleaching[7]andferricsulphateleaching[8]ofchalcopyrite. The objective of this study was to investigate and develop a simple, economically viable and environmentally friendly ferric leaching process for arseniccontaining copper concentrates under conditionssimilartotheGalvanoxprocess[9],employingactivatedcarbonascatalyst.

EXPERIMENTAL
Enargitesamplesusedinthisstudywerefromfourdifferentsourcesinthreecountries:anenargite sample fromthe UnitedStates(abbreviatedasS1), two floatation concentrates from Peru(S2and S4) and another floatation concentrate from a mine in Chile (S3). Some of the mineralogical and elementalcharacteristicsofthesesamplesaregiveninTable1.Inthistable,othercoppersulphides such as tennantite, covellite, chalcocite, bornite and chalcopyrite are referred to as other copper containingminerals. Table 1 Approximate percentages of important mineralogical and elemental constituents of the enargitesamples
Mineral/Element Enargite Pyrite S1 (wt.%) 62 16 S2 (wt.%) 20 62 7 16 27 5 S3 (wt.%) 23 54 0 12 26 4 S4(wt.%) 44 34 13 28 15 9

Othercoppercontainingminerals 12 Copper Iron Arsenic 38 7 12

Fourdifferenttypesofactivatedcarbonwereusedinthisstudy:genericactivatedcarbongranules (abbreviatedasGC),NORITGCA612(abbreviatedasNC),NORITDARCOH2S(abbreviatedas NC2)andCALGONCPGLF12x40(abbreviatedasCC).Forthesakeofbrevity,carbonalways referstoactivatedcarboninthisarticle. Batch leaching tests were carried out in 3L jacketed glass stirredtank reactors (Applikon Biotechnology)whichweresealedandequippedwithtwostainlesssteelpitchedbladeimpellers and three baffles. The stirrer speed was controlled at a constant value throughout each test. Temperature was maintained at 80C in all experiments using a Haake DC10P14 open bath circulator. Each reactor was also equipped with three probes: a thermocouple (Omega), a glass pHsensor(Applikon)andaAg/AgClreferenceelectrodeformeasuringsolutionredoxpotential (Analytical Sensors). The measured values of the probes were displayed by an Applikon bio controllerADI1030andrecordedbyacomputer.Aredoxpotentialsetpointwasdefinedinthe controller for each test. Whenever the solution redox potential fell below the setpoint, a signal was sent by the biocontroller to an Aalborg mass flow controller to sparge oxygen with 99.5% purity into the reactor. Excess oxygen exited the reactor through a condenser to minimise evaporationofwater. Theleachingsolutionconsistedofdeionisedwater,sulphuricacid(97%purity)andreagentgrades offerroussulphate(FeSO4*7H2O)andferricsulphate[Fe2(SO4)3*5H2O].Whenthetemperatureand the redox potential of the solution reached the desired values the test was started by adding an enargitesampleandactivatedcarbonatthesametime.AlltestswereconductedunderGalvanox process conditions [9], which are presented in Table 2. Solution samples (about 2 cm3 each) were taken at different times during the test and analysed for copper using an atomic absorption spectrometer. At the end of each test the remaining carbon particles were separated from the leachingresidueandwashedusingaUSAstandardtestsieve(no.25).Thentheyweredriedinan oven and weighed. The remaining contents of the reactor were also filtered through 1m filter paper, using a vacuum pump. The obtained solid residue of each test was dried, weighed and a representativesampleofitwassenttoalocallaboratoryforcopperassay.

Table2Experimentalconditionsforthe25testspresentedinthisstudy
Test ID Enargite sample type S1/B S2/A S3/A S4/A S1/B S2/A S3/A S4/A S1/B S1/B S1/B S2/B S2/B S2/B S4/A S4/A S4/A S4/A S4/A S2/B S2/B S1/B S1/B S1/B S1/B Enargite sample mass (g) 15 40 50 60 15 40 50 60 15 15 15 40 40 40 54 46.5 41 60 60 40 40 15 15 15 15 Carbon type Carbon mass (g) Initial acid amount (g) 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 Deionised water mass (g) 1500 1500 1500 1500 1500 1500 1500 1500 1500 1500 1500 1500 1500 1500 1500 1500 1500 1500 1500 1500 1500 1500 1500 1500 1500 Initial total iron content (g) 25.5 26.8 26.8 2.7 25.5 26.9 26.8 2.7 25.5 25.5 25.5 26.8 26.8 26.8 2.7 2.7 2.7 2.7 2.7 26.8 26.8 0 2.7 9 27 Redox potential setpoint (mVvs. Ag/AgCl) 485 490 515 515 485 490 515 515 485 485 485 515 515 515 515 515 515 515 515 490 490 515 515 515 515 Temperature (C) Stirrer speed (rpm)

A B C D E F G H I J K L M N O P Q R S T U V W X Y

GC/0 GC/0 GC/0 NC/0 NC/0 NC2/0 CC/0 GC/0 GC/0 GC/0 NC/1 NC/2 NC/3 NC/0 NC/0 GC/0 NC/0 NC/0 NC/0 NC/0

15 40 50 60 15 15 15 40 20 10 54 46.5 41 60 60 40 15 15 15 15

80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80

1200 1200 1200 1000 1200 1200 1200 1000 1200 1200 1200 1200 1200 1200 1000 1000 1000 800 1200 1200 1200 1200 1200 1200 1200

A means the enargite sample was used as received and B means it was (re)ground The corresponding numbers show how many times the carbon particles used in each test have been recycled

RESULTSANDDISCUSSION
TheEffectsofdifferentparametersonleachingofcopperfromenargitesamplesinthepresenceof activatedcarbonwerestudied.Thispaperdiscussesthe25mostindustriallyrelevantexperiments conductedtoexploretheinfluenceofsevenvariablesonenargiteleaching.Someofthesevariables areconcernedwithactivatedcarbonaddition,type,amountandrecycling.Othersexaminestirring speed,floatationconcentrateregrindingandinitialtotalironmass.

Effectofactivatedcarbonaddition
The effect of addingactivated carbonas acatalyst was studied by performing leaching testson four different enargite samples with and without activated carbon. The results are shown in Figure 1. A carbon to enargite sample mass ratio of 1 was used for all carboncontaining experiments(EH).AscanbeseeninFigure1,carbonhadahugeeffectonthecopperextraction from these samples. Copper leaching from enargite samples S1 and S2 without using activated carbondidnotachievemorethan35%and25%extractionrespectivelywithin70hours(testsA andB);butbyemployingacarboncatalyst(testsEandF)virtuallycompleteleachingofcopper wasachievedinabout45hours.

100 90

Copper extraction (%)

80 70 60 50 40 30 20 10 0 0 10 20 30 40 50

A - S1 B - S2 C - S3 D - S4 E - S1 + GC F - S2 + GC G - S3 + GC H - S4 + NC

60

70

Time (hours)

Figure1Effectofactivatedcarbonadditiononcopperextractionfromfourdifferentenargitesamples

TheleachingcurveoftestAhasreachedaplateauduetotheformationofasulfurlayeraround coppersulphideparticlesduringleaching(accordingtoEq.1),whichhinderscopperdissolution. ThelayercanbeidentifiedinFigure2,whichisanSEMimageoftheleachingresidueoftestA.It showsacrosssectionofanenargiteparticlethatstillcontainsalargeproportionofenargitedue to formation of the sulfur layer. The presence of enargite in the particle was verified by EDX analysis.AssumingthattestBwillreachitsmaximumcopperextraction,theleachingkineticsof testFis6timesfaster.

Figure2SEMimageofacrosssectionofahalfleachedenargiteparticlefromtestAresidue

Shorterleachingtime(lessthan24h)wasobtainedatahigherpotential(515mVvs.Ag/AgCl)for leachingenargitesamplesS3andS4usingactivatedcarbon(testsGandH).Duringthatperiodof time, in the absence of carbon, less than 20% and 73% of the copper extraction was achieved for testsCandDrespectively.

Effectofactivatedcarbontype
Inordertoinvestigatethereproducibilityofthecatalyticeffectofactivatedcarbon,fourdifferent typesofactivatedcarbonwereusedinleachingexperimentsofenargitesampleS1.Theresultsof these tests, as well as that for test A (no carbon), are shown in Figure 3. All types of activated carbon had a significant effect on the kinetics of leaching. GC (generic activated carbon) and NC (NORITGCA612),whichwerecoconutbasedactivatedcarbons,wereparticularlyeffective.NC2 (NORITDARCOH2S),whichwasusedintestJ,provedtobebetterthanNCinthefirsthalfofthe testbutitsperformanceslightlydiminishedintherestoftheexperiment,probablyduetolosingits integrity under agitation. CC (CALGON CPG LF 12x40), which was the least desirable carbon amongthefour,yieldedabout88%copperextractionin48hours(testK).Allactivatedcarbontypes exhibitedexcellentcatalyticbehaviourforleachingenargiteinironsulphatemedia.
100 90

Copper extraction (%)

80 70 60 50 40 30 20 10 0 0 10 20 30 40 50 60 A - S1 E - S1 + GC I - S1 + NC J - S1 + NC2 K - S1 + CC

Time (hours)

Figure3EffectofdifferenttypesofactivatedcarbonontheleachingofenargitesampleS1

Effectoftheamountofactivatedcarbonadded
Leaching tests L, M and N, using enargite concentrate S2 and generic activated carbon, were conducted at various carbon:concentrate mass ratios while other parameters were kept constant (seeTable2).TheresultsoftheseexperimentsarepresentedinFigure4.IntestL,inwhichthemass ratio of carbon to concentrate was 1 (carbon:enargite mass ratio of 5), extraction was almost completeafterabout15h(basedontheslopeofthecurveofthistestandthegeneralbehaviourof theothertwotests).TestM,withacarbon:concentratemassratioof0.5(carbon:enargiteratioof2.5) reached completion within 24 h. Test N with a carbon:concentrate ratio of 0.25 (carbon:enargite ratio of 1.25) concluded after about 30 h. Therefore, acceptable leaching performance can be achievedatcarbontoenargiteconcentrate(S2)ratiosaslowas0.25.
100 90

Copper extraction (%)

80 70 60 50 40 30 20 10 0 0 5 10 15 20 25 30 35 L - S2 1:1 GC M - S2 2:1 GC N - S2 4:1 GC

Time (hours)

Figure4Effectofamountofactivatedcarbonontheleachingofenargiteconcentrate S2at515mVvs.Ag/AgCl

Effectofactivatedcarbonrecycle
Inordertominimisethecostofactivatedcarboninthisleachingsystem,recyclingofcarbonwas consideredandstudied.Theresultsoffourtests(H,O,PandQ),focussedonthisfactorcanbeseen inFigure5.
100 90

Copper extraction (%)

80 70 60 50 40 30 20 10 0 0 5 10 15 20 25 30 H - S4, 1:1 fresh NC O - S4, 1:1 NC recycle from H P - S4, 1:1 NC recycle from O Q - S4, 1:1 NC recycle from P

Time (hours)

Figure5EffectofrecyclingactivatedcarbonontheleachingofenargiteconcentrateS4at1000rpm

Enargite concentrate S4 was used in these tests with a stirring speed of 1000 rpm. The activated carbonparticlesaftereachtestwereseparated,driedandweighed.Theconcentrate:carbonratioin thesefourtestswere1.FreshNORITGCA612carbonusedintestH.Eachsubsequenttestused thecarbonrecoveredfromthepreviousexperiment(i.e.thatfromHwasusedinO).Asshownin Figure5,rapidleachingkineticsaremaintainedaftereachrecycle.

Effectofstirringspeed
Figure6showstheleachingcurvesoftestsH,RandS.InthesetestsconcentrateS4wasleachedin thepresenceofNORITGCA612carbonatimpellerspeedsof800,1000and1200rpm.Thecurves indicatethatincreasingtheimpellerspeedfrom800to1000rpmhadmoreimpactontheleaching kineticsthanincreasingitfrom1000to1200rpm.
100 90

Copper extraction (%)

80 70 60 50 40 30 20 10 0 0 5 10 15 20 25 30 H - S4 + NC at 1000 rpm R - S4 + NC at 800 rpm S - S4 + NC at 1200 rpm

Time (hours)

Figure6EffectofstirringspeedontheleachingofenargiteconcentrateS4

Effectofenargiteconcentrateregrinding
Concentrate S2 was reground in a laboratoryscale ring mill for 90 seconds. The reground concentratewasthenleachedwithandwithoutactivatedcarbon(testsTandU).Figure7showsthe comparison of the results of these two tests and also the results of leaching concentrate S2 as receivedwithandwithoutactivatedcarbon(testsBandF).Theresultssuggestthatregrindinghas asignificanteffectonleachingwithoutacatalystbutactivatedcarbonwillcatalysebothasreceived andregroundconcentrateleachingtopracticallythesameextent.Thismaybeinterestingfroman industrial point of view, since using activated carbon can eliminate the need for regrinding to obtainfasterleachingkinetics.

100 90

Copper extraction (%)

80 70 60 50 40 30 20 10 0 0 10 20 30 40 50 60 70 B - S2 T - S2 (reground) F - S2 + GC U - S2 (reground) + GC

Time (hours)

Figure7LeachingofasreceivedandregroundconcentrateS4withandwithoutactivatedcarbon

Effectofinitialtotaliron
Fourdifferenttests(V,W,XandY)wereconductedtoexaminetheeffectoftheinitialmassoftotal iron. Ferric and ferrous sulphate salts were the source of initial iron in the leaching solution. In ordertoobtainanidenticalsolutionpotentialvalue(515mVvs.Ag/AgCl)forthetestsW,XandY, ironsulphatesaltswereaddedattheferric:ferrousratioof0.88.Theinitialtotalironamountforthe testsV,W,XandYwere0,2.7,9and27grespectively.TheresultsarepresentedinFigure8.All testscontainingaddedironoutperformedtestV.Theresultsshowthattheinitialconcentrationof totalironcanbeaslowasabout2g/Lwithoutimpedingtheleachingbehaviour.
100 90

Copper extraction (%)

80 70 60 50 40 30 20 10 0 0 5 10 15 V - S1 + NC (no iron added) W - S1 + NC (2.7 g total iron) X - S1 + NC (9 g total iron) Y - S1 + NC (27 g total iron) 20 25 30

Time (hours)

Figure8EffectofinitialtotalironcontentontheleachingofconcentrateS1

Carbonlossduringleachingtests
Activated carbon particles experience erosion under agitation conditions which leads to some amountsofcarbonlossattheendofeachtest.Asmentionedpreviously,afterfinishingeachtestthe remainingcarbonparticleswereseparated,washed,driedandweighedtofindthedegreeofcarbon loss. The carbon loss values for NORIT GCA 612 after the first and subsequent recycle tests

(H, O, P and Q) after 26 h and at 1000 rpm can be found in Figure 9. The average carbon loss is about10%ineachrecyclewithnosignificantdeclineinleachingkinetics(seeFigure5). Also carbon loss values for fresh NORIT GCA 612 and after 26 h at three different stirring speeds (tests H, R and S) are shown in Figure 10. Reducing the speed to 800 rpm significantly decreasedthecarbonloss(5%oftheinitialcarbonamount)whilehavingonlyaminoreffecton leaching(seeFigure6). Ingeneral,themeasuredcarbonlossvaluesseemtobeverypromising.Itisworthmentioningthat thelossisexpectedtobelowerinlargertanks.
20

Carbon loss (%)

15 10

5 0 0 1 2 Number of recycles 3

Figure9CarbonlossvaluesforNORITGCA612carbonparticlesaftereachrecycle, after26hoursat1000rpm

30 25
Carbon loss (% )

20 15 10 5 0 0 200 400 600 800 1000 1200 1400

Stirring speed (rpm)

Figure10Carbonlossvs.stirringspeedforNORITGCA612after26hours

CONCLUSIONS
Activatedcarbonwassuccessfullyusedinthisstudytocatalysetheferricleachingoffourdifferent enargite samples under the Galvanox process conditions. NORIT GCA 612, a granulated activated carbon based on coconut shells, proved the most effective of all activated carbon types tested. Investigating the effect of carbon amount on leaching of an enargite concentrate revealed that reducing the carbon:concentrate ratio to 0.25 (carbon:enargite ratio of 1.25) still produced 10

acceptableleachingperformance.Activatedcarbonrecoveredfromonetestwasrecycledtoseveral subsequenttestswithvirtuallythesameleachingrate.Loweringthestirringspeedfrom1200rpm to800rpmhadaminoreffectonleachingratebutgreatlydecreasedcarbonlossfrom26%to5%of theinitialcarbonmass.Thecarbonlossvaluesareexpectedtobelowerinlargertanks.Also,itwas observed that the use of activated carbon renders regrinding the concentrate unnecessary, since carboncatalysesbothasreceivedandregroundconcentrateleachingtopracticallythesameextent. Typically, virtually complete copper extraction from enargite concentrates was achieved with an initialtotalironconcentrationof2g/Lat515mV(vs.Ag/AgCl)inlessthan24hoursinthepresence ofactivatedcarbon.

ACKNOWLEDGMENTS
The authors would like to acknowledge the financial support of the Natural Sciences and Engineering Research Council of Canada through NSERC IdeatoInnovation Phase 2 Grant I2IPJ35026807.

REFERENCES
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