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A New Technology for Copper Slag Reduction to Get Molten Iron and Copper Matte
JOURNALOFIRON ANDSTEELRESEARCH,INTERNATIONAL２ ０ １ ５,２ ２( ５):３ ９ ６ Ｇ ４ ０ １
ANewTe chno l o o rCoppe rS l a du c t i ont oGe tMo l t e n g yf gRe I r onandCoppe rMa t t e JunZHANG, Yuan Ｇ hong QI, Di ng Ｇ l i uYAN, Ha i Ｇ chuanXU
( S t a t eKeyLabo r a t o r fAdvanc edS t e e lPr o c e s s e sandPr oduc t s,Cen t r a lI r onandS t e e l yo Re s e a r chI ns t i t u t e,Be i i ng１０００８１,Ch i na) j Ab s t r a c t:Thechangeo fi r onc ompo s i t i ona swe l la st her emova lo fc oppe rf r omi r onwa si nve s t i t edi nt her educ t i on ga r o c e s s,andanew wayt ode a lwi t hc oppe rs l agwa sp r opo s ed．Thei r oni nc oppe rs l agex i s t sma i n l nt hef o rmo f p yi f aya l i t e,andt hec oppe rsu l f i dec on t en ta c c oun t sf o rj us tabou t５０％．The r e f o r e,t hemagne t i cs epa r a t i ona swe l la s r i nd i ngf l oa t a t i onme t hodi sno tsu i t ab l e,andapy r ogen i ct r e a tmen tonc oppe rs l agi sne c e s s a r a r bu r i z a t i on g y．Thec andde su l f u r i z a t i onp r o c e s si sr e s t r i c t edt oadeg r e ewi t h i nt hec a r bonc ompo s i t epe l l e t s,andc oppe rma t t epha s ep r e Ｇ c i i t a t e sf r omc oppe rs l agi nt her educ t i onp r o c e s s,wh i chi simmi s c i b l ewi t h mo l t eni r onands l ag．Thec oppe rc on Ｇ p t en tde c r e a s e st o０ ４％ a st hec a r bonc on t en ti n mo l t eni r onr e a che s３ ８４％ ,andt her emova lr a t i oo fc oppe rf r om mo l t eni r onapp r oa che st o８０％．Ther educ t i onandsu l f u r i z a t i onp r o c e s sc anbec omp l e t edi nones t ep,andt hec oppe r i ss epa r a t edf r omi r onba s edont het e r na r s t emo fi r on Ｇma t t e Ｇ s l ag． ysy Ke r d s:c oppe rs l ag;r educ t i on;su l f u r i z a t i on;ma t t e ywo
Py r ome t a l l u r st he mo s timpo r t an tp r o c e s s gyi f o rc oppe rsme l t i ngcu r r en t l heou t tby wh i ch y,t pu [] a c c oun t sf o r８０％ o ft het o t a l,even９７％i nCh i na１ ． They i e l do fc oppe rs l agi s２ ２tpe rt onc oppe r, i r on a swe l la scoppe rc on t en t so fwh i cha r e３０％ －４０％ [ ２] and０ ５％ －２ ０％ ,r e spe c t i ve l r e f o r e,s i Ｇ y ．The g n i f i c an te conomi cbene f i t s wi l lbea c i r edv i at he qu r e c l eo fcoppe rs l ag． yc Thewaysf o rc oppe rs l agu t i l i z a t i oni nc l udef i r e d i l u t i on and g r i nd i ng f l oa t a t i on．Thef i r ed i l u t i on me t hodl owe r st hec oppe rd i s s o l u t i onc on t en ti ns l ag v i ar educ t i onandsu l f i d i z a t i on,andc oppe ri sr e c ov Ｇ [ ３ Ｇ ６] , e r edi nt hef o rmo fsu l f i de s t hey i e l do fwh i chi s [] r e l a t i ve l ow ４ ．Theg r i nd i ngf l oa t a t i ont e chno l ogy yl [ ] i sma i n l i c a lt r e a tmen tp r o c e s s７Ｇ１１ ,wh i chi s yaphys us e f u lf o rr e c l eo fme t a l l i cc oppe randc oppe rsu l Ｇ yc f i de pha s e s,bu ti nc apab l eo f ox i de s．The r e f o r e,
cu l t,bo t ho fwh i cha r ecomp l e t e l s c i b l e．Hue t y mi [ ] a l １２ i nve s t i t edt hef e a s i b i l i t fcoppe ri nCu２OＧ ga yo FeO s t em wi t h CaCl２ ,andt her emova lr a t eo f ys coppe rr e a ched５５ ５％ whenhe l da t１０００ ℃f o r４h． Mo r eove r,t he coppe rr emova lr a t er e a ched ７０％ wh i l ehe l da t１０００ ℃ f o r１５ mi n,whenFeOＧS iO２Ｇ [ [ ] １３] CaCl２ compoundf l ux wa sus ed ．Wange ta l １４ s t ud i edt heequ i l i br i um o f Fe ＧS ＧC s t em;i t wa s ys f oundt ha tCandS we r eexc l us i vet oe a cho t he ri n mo l t eni r on,anda mi s c i b l e gapf o rmed whent he c a rboncon t en ti ni r onwa sh i r eove r, ghenough．Mo
t hee f f e c to fa l ka l i neo ra l ka l i nee a r t hsu l f i de son [ ] １５, coppe rr emova lf r om mo l t eni r on wa ss t ud i ed １６ , wh i chenhanc edt hed i s t r i bu t i onr a t i oo fc opp e rb e Ｇ [ ] twe e nma t t eand mo l t e ni r on．Be s i d e s,Longe ta l １７ r epa r edt heMo ＧFea l l oyf r omcoppe rs l agt hr ougha p two Ｇ s t ep me t hod,and coppe r wa sr emovedf r om mo l t eni r oni nt hef o rmo fcoppe rsu l f i de s,wi t had Ｇ bo t hf i r ed i l u t i onand g r i nd i ngf l oa t a t i ont e chno l o Ｇ ; , i t i ono fFeS ＧNa２Sf l ux f i na l l hecoppe rcon t en t yt i e sa r es e l e c t i vet ot he mo r l ogy o f mi ne r a l s． d g pho [ ] ni r ond e c r e a s e dt o０ １％． I na dd i t i on,Yama c h i１８ Mo s timpo r t an t l hei r oni sno tr e c l edv i at he i gu y,t yc t ud i e dt hec opp e rr emov a lf r om c a r bons a t u r a t e di r on two ways, wh i chi ss t i l li ns l ag．The r e f o r e,t he s , me l twi t hanox i da t i on me t hod wh i chadop t ed Ag t ho r oughr educ t i ono fc oppe rs l agi sne c e s s a r y． smed i um pha s eandB２O３ a spa r en tpha s e． Thes epa r a t i ono fc oppe rf r omi r onme l ti sd i f f i Ｇ a Founda t i onI t em: I t em Spons o r edbyNa t i ona lNa t ur a lSc i enc eFounda t i ono fCh i na ( ５１４０４０７５) B i o r aphy: JunZHANG,Do c t o r; E Ｇma i l: z x t ４２４＠１６３ c om Re c e i v e dDa t e:Do c embe r１６,２０１３ j g
I s sue５ A New Te chno l ogyf o rCoppe rS l agReduc t i ont oGe tMo l t enI r onandCoppe rMa t t e
３９７
I nt hep r e s en two rk,t hec oppe rs l ag wa sr e Ｇ duc edi nt hef o rm o fc a rbonc ompo s i t epe l l e t s,and mo l t eni r ona swe l la sc oppe rma t t ewa sa c i r edi n qu one Ｇ s t ep．Thus,t her emova lo fc oppe rf r om i r on wa sr e a l i z edi nt her educ t i onp r o c e s s． F i na l l y,anew t e chno l ogyf o rc oppe rs l agr e c l eba s edont het e r Ｇ yc na r t emo fi r on Ｇma t t e Ｇ s l ag wa sp r opo s ed． ys ys
l l e t swe r el oadedi naco rundumd i s cwi t had i ame Ｇ pe t e ro f５０mm,wh i chwa st henhe l da t１１００and１３５０ ℃f o r３０ mi n,r e s e c t i v e l i n a l l hes amp l e wa s p y．F y,t d r awnou to ft het ubeandcoo l eddowni na i ra tt he endo ft hehe a t i ng s t age．Thecompos i t i ono fi r on nugge t swa sde t e rmi nedt hr ought hechemi c a lt i t r a Ｇ t i onana l i s,andt hei r ony i e l do fs amp l e swa sde Ｇ ys t e rmi neda sf o l l ows． １ Exp e r imen t a l m ( η＝ ×１００％ １) m０ １ １ Ma t e r i a l s r e,ηi st hei r ony i e l d,％ ;m i st hema s so fi r on Thecompo s i t i onso ft hec oppe rs l agandc oa l whe , ; t g andm０i st hema s so ft o t a li r oni ns amＧ us eda r eg i veni nTab l e s１and２,r e spe c t i ve l y,and nugge l e,g． t he i rpa r t i c l es i z ei sbe twe en０ ０７４and０ １５０ mm． p Be s i de s,pur echemi c a lr e agen t so fr educ edi r onand ４ S e r a t i onbe twe enc oppe randmo l t eni r on r aph i t epowde rwe r ei nvo l vedi nt hep r e s en two rk． １ pa g Theg r aph i t ec ruc i b l el oadedwi t hs amp l e swa s Thei ng r ed i en t sa c c o r d i ng t or equ i r ed r a t i o s , l da t１３５０ ℃f o r１０－４０mi nd i r e c t l rN２a t Ｇ yunde we r e we i i ng an e l e c t r on i c ba l anc e wh i ch he ghed us mosphe r e,andt hec a rbonandcoppe rcon t en t swe r e we r et henmi xedandpr e s s edi n t oc l i nd r i c a ls amp l e s y t e rmi ned by chemi c a lt i t r a t i onana l i s;f i na l l ys y, wi t hama s so f９ ０gandxC/xO o f１ ５．Thes amp l e s de
we r ed r i edi nane l e c t r i cb l a s td r i ngovena t２００ ℃ y f o r６０ mi n． Tab l e１ Ch emi c a lc ompo s i t i ono ft h ec opp e rs l a s s％ g ma TFe
Cu
S
FeO
４０ ５７ ０ ７５ ０ ７８ ４２ ７４
S iO２
CaO
３２ ７６ ３ ８４
MgO
１ ０４
Al２O３ ３ ８７
Tab l e２ Pr ox ima t eana l s i so fc o a l ma s s％ y Mo i s t ur e ０ ８６
Vo l a t i l e ５ ６２
Ash
１９ ８４
F i xedc a r bon ７３ ６８
１ ２ Chemi c a l pha s e sand mi c r o s c op i cana l s i so f y c oppe rs l a g Thechemi c a lpha s e so fc oppe rs l ag we r ede t e r Ｇ mi nedv i at hel e a ch i ngandchemi c a lt i t r a t i onana l Ｇ y s i s me t hod．Thepa r t i c l e so fc oppe rs l ag we r ec onＧ s o l i da t edbye e s i nw i t hqu a d r o la sc u r i nga e n ti n poxyr g amo l d,wh i ch wa smadei n t oanop t i c a ls l i c eonan e l e c t r i crubb i ng and po l i sh i ng ma ch i ne．The s l i c e , wa sobs e r vedbys c ann i nge l e c t r onmi c r o s c opy wi t h a magn i f i c a t i ont ime so f２０００i nt heba cks c a t t e r ed t t e rn,andt he mi c r o Ｇ a r e ac ompo s i t i onana l i so f pa ys s amp l ewa sc onduc t edt hr oughaspe c t r ome t e rc on Ｇ ne c t edt oi t． １ ３ Re du c t i on and sme l t i ng Ｇ s e r a t i on o fc oppe r pa s l a t h i nc a r bonc ompo s i t epe l l e t s gwi Ther educ t i onandsme l t i ng Ｇ s epa r a t i ono fc op Ｇ rs l agwa sc onduc t edi nadoub l e Ｇ t empe r a t u r ez one pe r e s i s t anc ef u rna c e unde r N２ a tmo sphe r e．The d r y
t her a t i oo fcoppe rr emova lf r omi r onnugge twa sde Ｇ f i neda sf o l l ows． CCu ( rCu＝１００－w TFe ０ /１００ ２) CCu st her a t i oo fcoppe rr emova lf r omi r on, whe r e,rCui ％ ;w TFei st o t a li r oncon t en to ft heo r i i n a l s a m l e, g p ０ ; ％ CCui st hecoppe rcon t en ti nt heo r i i na ls amp l e, g st hecoppe rcon t en ti ni r onnugge t,％． ％ ;andCCui
２ Re s u l t s
２ １ Ch emi c a lpha s e sa ndmi c r o s t r u c t u r eo fc o e rs l a pp g Thechemi c a lpha s ecompos i t i ono fCuandFeo f coppe rs l agi sg i veni nTab l e３． I tc anbes e ent ha t, t hei r on ma i n l i s t si nt hef o rm o ff aya l i t e,and yex t heamoun to fFeandFe３O４i ssma l l． I tme anst ha t t her e c l eo fi r onf r om coppe rs l ag v i a magne t i c yc s epa r a t i onme t hodi sno tapp l i c ab l e． Tab l e３ Ch emi c a lpha s eana l s i so fc opp e rs l a y g ％
I r on Ｇ be a r i ngpha s e
Coppe r Ｇ be a r i ngpha s e
iO２＋FeS ２FeOS
９２ ０５
Fe
０ ６４
Fe３O４
CuSO４
７ ２８ ８ ９２
Cu２O
３９ ９０
Cu
０ ７６
Cu２S
５０ ４２
Themi c r o Ｇmo r l ogyo fcoppe rs l agv i aSEM pho , obs e r va t i oni sg i veni nF i １ a n dr e l e v a n t c h emi c a l g compos i t i ono fs e l e c t ed pha s e s wa sde t e rmi ned by spe c t rum ana l i s,t her e su l to f wh i chi sg i veni n ys Tab l e４． I tc anbes e ent ha t,t hec opp e rma t t ep a r t i c l e
J ou r na lo fI r onandS t e e lRe s e a r ch,I n t e r na t i ona l Vo l ２２
３９８
i swr appeda r oundbyt heg l a s s s e,andt hepa r Ｇ ypha t i c l es i z ei ssosma l l( abou t６０μm)t ha tah i hr e g Ｇ i r emen tong r i nd i ngs i z ei sdemandedwheng r i nd Ｇ qu i ngf l oa t a t i onp r oc e s si sadop t ed．Mo r eove r,t hecop Ｇ rsu l f i de sa c coun tf o rj us tabou taha l fa c co rd i ngt o pe , Tab l e３．Tha ti s t her e cove r a t eo fcoppe rv i a yr r i nd i ngf l oa t a t i oni sno mo r et han５０％．I no t he r g wo rds,t heg r i nd i ngf l oa t a t i onp r oc e s si sno tagood cho i c ef o rcoppe rr e c l e． yc ２ ２ Re du c t i on and sme l t i ng Ｇ s e r a t i on o fc oppe r pa s l a t h i nc a r bonc ompo s i t epe l l e t s gwi Theg r a so fs amp l e sa f t e rr educ t i onandsme l t Ｇ ph
F i １ SEMima eo fc opp e rs l a g g g
Tab l e４ Sp e c t r umana l s i so fpo i n t s１and２i nF i １ ma s s％ y g
Po i n t
Po i n t１ Po i n t２
Ra t i o
S
Pb
Ma s sr a t i o
２０ ６４
１１ ８６
Ma s sr a t i o
０ ８０
３ ０２
Mo l a rr a t i o Mo l a rr a t i o
３５ ７６ ０ ７２
３ １８ ０ ４２
Fe
１７ １７
１７ ０７
３７ ９３
１９ ５１
Cu
５０ ３３
４３ ９９
O
Mg
Al
S i
K
Ca
Zn
２８ ５２
１ ２６
２ ５７
１９ ８１
０ ８０
２ ４４
２ ３１
５１ ２０
１ ４９
２ ７４
１９ ８１
０ ５８
１ ７５
１ ０１
i ng Ｇ s epa r a t i ona r eshowni nF i ２．I tc an bes e en pe a r si nt her educ t i onp r oc e s s． g , t ha tt he r ei sr edpowde r sp r e c i i t a t edf r om c oppe r The mi n e r a lc ompo s i t i ono ft her e dpowd e r swa s p s l agi nt her educ t i onpr o c e s s． de t e rmi ned by XＧ r ay d i f f r a c t i on (XRD)ana l i s, ys Theave r agec a rbonandc oppe rc on t en t so ft he andt her e su l ti sg i veni nF i ３．Hema t i t ewa sde t e r Ｇ g , , r edpowde rmi x t u r ewe r e６４ ５％ and０ ３％ r e spe c Ｇ mi nedi nt hepowde r s wh i chexp l a i nedt heco l o ro f t i ve l ti s,t hec oppe rc on t en ti sapp r ox ima t e l r s,andal i t t l eFeandCuO we r ea l sof ound． y．Tha y powde ０ ８５％i ft hec a rboni sexc l uded．The r e f o r e,anew Mo r eove r,ani so l ogue mi ne r a lo fA,wh i ch maybe , , , s ed i f f e r en tf r om t he mo l t ens l ag andi r onap Ｇ i nc l ude sFe３O４ MgFe２O４ CoFe２O４ Cu１２Mn１８O４ pha
( a)R ＝０ ３; ( b)R ＝０ ５; ( c)R ＝０ ８; ( d)R ＝１ ０．
F i ２ Ef f e c to fba s i c i t l t i ng Ｇ s epa r a t i onp r o c e s so fc opp e rs l a g yR onsme g
F i ３ XRDpa t t e rno ft h er e dpowd e r s g
andCuMn２O４ ,e t c ,wa sf ound．The s eox i de scou l d , no tex i s ti nt her educ t i onp r oc e s s wh i chmos tl i ke l y f o rmeda tt hecoo l i ngs t agei nt hea i r．The r e f o r e,i t c anbet hough tt ha tt her ed powde r sa r econve r t ed f r omt hema t t epha s e． Thee f f e c to fba s i c i t l f urandc a rboncon Ｇ yonsu t en t so fi r onnugge ti sshowni nF i ４． I t c a nb e s e e n g t ha t,t hesu l f urcon t en ti ni r onde c r e a s e s wi t hi n Ｇ c r e a s i ngba s i c i t fs amp l e,bu tt het r endi sno tob Ｇ yo v i ouswheni ti sbeyond０ ５．The r e f o r e,t her emova l o fsu l f urf romi ronnugge tv i af l uxi sr e s t r i c t edt oa
I s sue５ A New Te chno l ogyf o rCoppe rS l agReduc t i ont oGe tMo l t enI r onandCoppe rMa t t e
３９９
F i ５ Re l a t i on s h i e twe enc a r bonandc opp e r g pb c on t en t si ni r onnug e t g
F i ４ Ef f e c to fba s i c i t u l f u randc a r bon g yons c on t en t si ni r onnug e t g
deg r e e．Thec a rbonc on t e n ti sa lmo s tno ti n f l u e n c e dby , ba s i c i t w h i c hi sa r o u n d１ ２％． y
t i b l ei nt hei r on．
２ ３ Co e rr emo v a lf r ommo l t e ni r o ni nr e d u c t i o np r o c e s s pp Thechangeo fc a rbonandi r onc on t en t si ni r on wi t hho l d i ngt imei nt heg r aph i t ec ruc i b l ei sshown i nF i ５,whe r et heba s i c i t fs amp l e swa s１ ０． I t g yo c anbes e ent ha t,t hec a rbonc on t en ti nc r e a s e swi t h i nc r e a s i ngho l d i ngt ime,bu tt het r endf o rc oppe ri s i nve r s e,t hel owe s tc on t en to f wh i chi sj us tabou t , ０ ４％．Tha ti st hecoppe randc a rbona r ei ncompa Ｇ
３ １ Re du c t i ono fc oppe rs l a g Ther educ t i onr e a c t i onsi nvo l vedi ncoppe rs l ag a r el i s t edi nTab l e５． I tc anbes e ent ha tt hemi ne r a l s o fcoppe randi r ona r ee a s i l educ eda tasme l t i ng Ｇ yr r educ t i ont empe r a t ur e,wh i cht r ans f o rmi n t ome t a l Ｇ l i c pha s e s unde rr educ t i on cond i t i ons．The r e f o r e, t her educ t i ono fcoppe rs l agi st ho r oughno ma t t e r wha tk i ndo fmi n e r a l si sr e du c e d,wh i c he l imi n a t e st he
３ Di s c u s s i on
Tab l e５ Re du c t i onands u l f u r i z a t i onr e a c t i on si nc opp e rs l a g Re a c t i on
ΔGθ
/K Gene r a t i ngt empe r a t ur e
ΔGθ＝５７５４０－１６１T
３５７
CuSO４＋２C＝Cu＋２CO＋SO２
ΔG ＝６６９８２－３５４T
Fe３O４＋４C＝３Fe＋４CO ２FeOS iO２＋２CaO＋２C＝２Fe＋２CO＋２CaOS iO２
ΔGθ＝６５４８９９－６５９T
ΔGθ＝２０９７１１－３２５T
FeS＋CaO＋C＝Fe＋CO＋CaS
ΔGθ＝１４１３１０－１５４T
Cu２O＋C＝２Cu＋CO
Cu２S＋CaO＋C＝２Cu＋CO＋CaS
θ
ΔGθ＝１１６４７８－１２５T
４５１ ９９４ ６４５ ９３２ ９１８
１ ６％ whent he ba s i c i t s beyond ０ ５．Tha ti s, yi t he r ei snof ur t he rde su l f ur i z a t i ont hr oughs l agwhen ３ ２ Ca r bu r i z a t i onandd e s u l f u r i z a t i oni nr e du c t i on t hec a rboncon t en ti ni r oni sl ow,andaf ur t he rde Ｇ r o c e s s c r e a s eo fs u l f u rc o n t e n t m u s tb ee s t a b l i s h e do nt h e p I ti sknownf r om above Ｇmen t i onedr e su l t st ha t ba s i so fh i rc a rbur i z a t i oncon t en t．Thede su l f u Ｇ ghe i z a t i onp r oc e s so f mo l t eni r onc anbede s c r i beda s t he c a rbon c on t en to fi r on nugge ti sj us t abou t r １ ２％ ,a l t houghc oa li si nexc e s s． I tme anst ha tt he f o l l ows: ( Fe]＋ [ S]⇔ [ FeS] ３) c a rbu r i z a t i onp r o c e s si nt hec a rbonc ompo s i t epe l l e t [ FeS]＋ ( CaO)＋ [ C]＝ [ Fe]＋ ( CaS)＋CO ( ４) i sr e s t r i c t edt oac e r t a i ndeg r e e,wh i chha sbe end i s Ｇ [ [ ] cus s edi ne a r l i e rwo rk１９ ．Howeve r,t hec a rbonc on Ｇ Ther e a c t i on ( ３)move st owa rdt her i h td i r e c t i o n g , t en tc anr e a chah i l uei nt heg r aph i t ec ruc i b l e． whent hec a rboncon t en ti nc r e a s e s duet ot her epu l Ｇ ghva The r e f o r e,t hec a rbons a t u r a t i onc ond i t i onc anno tbe s i onbe twe enc a rbonandsu l f ur,andt hent hede su l Ｇ r e a l i z ed wi t h i nt he c a rbon c ompo s i t e pe l l e t s,and f ur i z a t i onp r oc e s soc cur sv i as l agi nt hef o rmo fr e a c Ｇ ( ) s omeme a sur e se l s emus tbet aken． t i on ４ ．Ast hec a rboncon t en tde c r e a s e st oac e r t a i n Thesu l f u rc on t en ti ni r oni si n f l uenc edbyt he deg r e e,t her e a c t i on ( ３)i sr e s t r i c t ed,andr e a c t i on ba s i c i t fs amp l e s;howe v e r,i ti sac on s t a n to fa bou t ( ４)c e a s e s． I tc anbet hough tt ha tt hede su l f ur i z a t i on yo r e s t r i c t i ononc ompo s i t i ono fc oppe rs l ag．
４００
J ou r na lo fI r onandS t e e lRe s e a r ch,I n t e r na t i ona l Vo l ２２
r o c e s soc cur sbe twe ent hepha s e so fs l agandma t t e． p Mo r eove r,t hef o rma t i ono fCu２Si sont heba s i so f FeSex i s t enc e． ( [ FeS]＋２[ Cu]＝ [ Fe]＋ [ Cu２S] ５) The r e f o r e,how t oc on t r o lt her educ t i ondeg r e eo f , FeSi sc r i t i c a l wh i chi sr e a l i z edbyad us t i ngt heba Ｇ j s i c i t fs l aga c c o r d i ngt or e a c t i on ( ４)． yo ３ ３ Coppe rr emo v a lf r om mo l t e ni r on Ther e l a t i onsh i twe enc a rbonc on t en tand p be c oppe rr emova lr a t ei sshowni nF i ６． I tc anbes e en g t ha tt her emova lr a t eo fc oppe rf r omi r oni nc r e a s e s wi t hi nc r e a s i ngt hec a rbonc on t en t,wh i chi sc l o s et o ８０％ whent hec a rbonc on t en ti s３ ８４％．
ob t a i nedi nones t ep．Ba s edont h i s,anewt e chno l o Ｇ t od e a lw i t hc o e rs l a a sd e i c t e di n F i ７i s gy pp g p g r opos ed．Thecoppe rs l a t hR ＝１ ０andxC/xO ＝ p gwi １ ５i sr educ edandsu l f ur i z edbyt hecoa li nc a rbon , compos i t epe l l e t sf i r s t l a n dt h e nt h es m e l t i n Ｇ ep Ｇ y gs a r a t i onp r oc e s si scomp l e t eda t１３５０ ℃i nasme l t e r f urna c e wi t hacokel aye r,wh i chi si n t r oduc eda s c a rbur i z i ngagen tt ome e tt hec a rbons a t ur a t i oncon Ｇ , d i t i oni n mo l t eni r on．F i na l l he mo l t eni r on wi t h y t coppe rcon t en tl owe rt han０ ４％ andc a rboncon t en t , c l os et o４％ i sob t a i ned andt hecoppe ry i e l dv i a ma t t eapp r oa che st o８０％．
F i ７ S ch ema t i cd i a r amf o rc opp e rmi n e r a lt r e a tmen t g g
４ Conc l u s i on s
F i ６ Ef f e c to fc a r bonc on t en tonc opp e rr emo v a l g
Almo s ta l lt h ec opp e rd i s s o l v e si nt h emo l t e ni r on wh e nt hes u l f u rc on t e n ti ni r oni sh i hec a rbon gh．Ast c on t en ti nc r e a s e s,t hec oppe ri nt hei r ont r ans f o rms i n t oma t t epha s eduet ot hei nc ompa t i b i l i t twe en ybe CandSi ni r on． F i na l l hec oppe ri sr emovedf r om y,t i r on．Thecoppe ri sr emovedf r om mo l t eni r oni nt he f o rmo fCu２S,noma t t e rwha tt hek i ndo ft heex i s t Ｇ enc ef o rm o fc oppe ri si nr aw ma t e r i a l s,wh i chen Ｇ su r e st heh i e c ove r a t eo fc oppe r． ghr yr
( １)Thei r oni nc opp e rs l a x i s t sma i n l nt he ge yi f o rmo ff aya l i t e,wh i chme anst ha tt hemagne t i cs ep Ｇ a r a t i oni sno tapp l i c ab l e．Thecoppe rsu l f i decon t en t , o ft hecoppe rs l agi sj us tabou t５０％ andt hecoppe r ma t t epa r t i c l e sa r esma l landwr appedbyt heg l a s s y s e．The r e f o r e,t he e f f e c to f coppe rr e cove r pha y , t hr ought heg r i nd i ngf l oa t a t i onme t hodi swe ak and t hepy r ogen i ct r e a tmen toncoppe rs l agi sne c e s s a r y． ( ２)Thec a r bu r i z a t i onc on t e n to fi r oni sr e s t r i c t e d , wi t h i nt hec a r bonc ompo s i t ep e l l e t s wh i c hi sj u s tabou t １ ２％ ,andt hesu l f urcon t en ti ni r on ma i n t a i nsa t １ ６％ whenba s i c i t sove r０ ５．Mo r eove r,t he r ei s yi ama t t epha s ebe a r i ngcoppe rp r e c i i t a t edf r om s l ag p i nt her educ t i on p r oc e s s,wh i chi simmi s c i b l e wi t h mo l t eni r onands l ag． ( ３)Thec opp e rc on t e n td e c r e a s e st o０ ４％ a st he c a rboncon t en ti n mo l t eni r onr e a che s３ ８４％ ,and t her emova lr a t i oo fcoppe rf r om mo l t eni r oni sc l os e , t o８０％ wh i chensur e sah i e cove r a t i oo fcop Ｇ ghr yr r．Be s i de s,t he de su l f ur i z a t i on o fi r oni s de t e r Ｇ pe mi nedbyt hec a rboncon t en twi t h i ni t,andt her e Ｇ duc t i ono fsu l f i de si supt ot heequ i l i br i um be twe en t hema t t eands l agpha s e s． ( ４)Anewp r oc e s st ode a lwi t hcoppe rs l agand conc en t r a t e s,wh i ch wa sba s edont het e rna r Ｇ ys ys , t emo fi r on Ｇma t t e Ｇ s l ag wa sp r opos ed．Ther educ t i on
３ ４ Pr opo s a lo fanewwa o rc oppe rs l a e c c l e yf gr y Di f f e r en tk i ndso fi r onandc oppe rmi ne r a l sd i s Ｇ t r i bu t eamongs l ag,ma t t eandi r onpha s e s,r e spe c Ｇ t i ve l t t e r wha tt hek i ndo fc oppe rs l agi s． y,no ma The r e f o r e,t hepr o c e s so fr educ t i onandsu l f u r i z a t i on i sj us tame anst ot r ans f e rt hemamongt he s epha s e s． The r ea r etwof a c t o r sf o rt hes epa r a t i ono fc oppe r f r omi r on:onei st hec a rbonc on t en to fi r on,andt he o t he ri st heex i s t enc eo fc oppe ri nt hef o rmo fCu２S． Thec a rbu r i z a t i onandsu l f u r i z a t i onc anbec omＧ , l e t eds imu l t aneous l nt her educ t i onp r o c e s s wi t h p yi noadd i t i ono fsu l f u r i z i ngr e agen t,andt hei r ona l l oy andsu l f ur i z a t i on p r oc e s si scomp l e t edi n ones t ep t h i nt hec a rboncompos i t epe l l e t s,andf ur t he rc a r Ｇ wi t hl owcoppe rc on t en ta swe l la sc oppe r ma t t ei s wi
I s sue５ A New Te chno l ogyf o rCoppe rS l agReduc t i ont oGe tMo l t enI r onandCoppe rMa t t e
bu r i z a t i on pr o c e edsi nt hesme l t e rf u rna c e wi t ha , c okel aye r． F i na l l t h em o l t e n i r o nw i t hc o e r c Ｇ y pp on t en tl owe rt han０ ４％ andc a rbonc on t en tc l o s et o ４％i sob t a i ned,andt hec oppe ry i e l dv i a ma t t eap Ｇ , r o a c h e s t o８ ０％ w h e nt h es a m l eo f R ＝１ ０a n d p p xC/xO ＝１ ５i she l da t１３５０ ℃． Re f e r enc e s: [ １] B．L i,H．Wang,J H．Hu,L．L i,Mi n i ngand Me t a l l ur gy１８ ( ２００９)No １,４４ Ｇ ４８． [ ２] J H．Hu,H．Wang,HL．L i u,L．L i,J our na lo fHunan Un i Ｇ ve r s i t fSc i enc eand Te chno l ogy,Na t ur a lSc i enc eEd i t i on２６ yo ( ２０１１)No ２,９７ Ｇ １００． [ ３] L N．Zhang,L．Zhang,MY．Wang,Z D．Su i,Non f e r r ous Me t a l s５７ ( ２００５)No ３,４４ Ｇ ４７． [ ４] HQ．Chen,P X．L i,S G．L i u,Z J． Zhang,HuNanNon f e r Ｇ r ousMe t a l s２２ ( ２００６)No ３,１６ Ｇ １８． [ ５] R G． Re ddy,V L． Pr a bhu,D．Ma n t h a,Mi n e r．Me t a l l． Pr o c e s s． ２３ ( ２００６)９７ Ｇ １０３． [ ６] S．Va i s bu r d,D G．Br a ndon,S．Ko z h akhme t o v,E．Ke n z h a l i e v, y Me t a l l．Ma t e r．Tr ans．B３３ ( ２００２)５６１ Ｇ ５６４．
４０１
[ ７] A． Sa r r a f i,B．Rahma t i,HR．Ha s s an i,HHA． Sh i r a z i,Mi n Ｇ e r．Eng． １７ ( ２００４)４５７ Ｇ ４５９． [ ８] WJ．Br u c k a r d,M．Some r v i l l e,F．Ha o,Mi n e r．Eng．１７ ( ２００４)
４９５ Ｇ ５０４． [ ９] R． J i n,J S．Wang,QR．Long,J i angx iNon f e r r ous Me t a l s２３ ( ２００９)No １,１２ Ｇ １４． [ １０] MA．We i,Mi n i ngand Me t a l l ur ２００４)No １,３８ Ｇ ４１． gy１３ ( [ １１] J A．Chen,E M．Gong,X B．L i,J．L i u,J our na lo fJ i angx i Un i ve r s i t fSc i enc eandTe chno l ogy３１ ( ２０１０)No ３,１９ Ｇ ２１． yo [ １２] X J．Hu,P G．J i ang,Z．Yan,L Q．Zhu,KC．Chou,H． Ma t suur a,F．Tsuk i ha sh i,I S I JI n t． ５３ ( ２０１３)５４１ Ｇ ５４３． [ １３] X J．Hu,Z．Yan,P G． J i ang,L Q． Zhu,K．Chou,H．Ma t Ｇ suur a,F．Tsuk i ha sh i,I S I JI n t． ５３ ( ２０１３)９２０ Ｇ ９２２． [ １４] C．Wang,J．Hi r ama,T．Naga s aka,S．Ban Ｇ S I JI n t．３１ ya,I ( １９９１)１２９２ Ｇ １２９９． [ １５] C．Wang,T．Naga s aka, M．Hi no,S．Ban Ｇ S I JI n t．３１ ya,I ( １９９１)１３００ Ｇ １３０８． [ s aka, M．Hi no,S．Ban Ｇ S I JI n t．３１ １６] C．Wang,T．Naga ya,I ( １９９１)１３０９ Ｇ １３１５． [ Pa l a c i o s,M． Sanche s,T．Mi k i,Y． Sa s ak i,M． １７] T V．Long,J． Hi no,I S I JI n t． ５２ ( ２０１２)１２１１ Ｇ １２１６． [ １８] K．Yamaguch i,H．Ono,I S I JI n t． ５２ ( ２０１２)１８ Ｇ ２５． [ １９] J． Zhang,YH．Qi,D L．Yan,X L．Cheng,P．He,J． I r on S t e e lRe s． I n t． ２２ ( ２０１５)１２１ Ｇ １２７．
JOURNALOFIRON ANDSTEELRESEARCH,INTERNATIONAL２ ０ １ ５,２ ２( ５):３ ９ ６ Ｇ ４ ０ １
ANewTe chno l o o rCoppe rS l a du c t i ont oGe tMo l t e n g yf gRe I r onandCoppe rMa t t e JunZHANG, Yuan Ｇ hong QI, Di ng Ｇ l i uYAN, Ha i Ｇ chuanXU
( S t a t eKeyLabo r a t o r fAdvanc edS t e e lPr o c e s s e sandPr oduc t s,Cen t r a lI r onandS t e e l yo Re s e a r chI ns t i t u t e,Be i i ng１０００８１,Ch i na) j Ab s t r a c t:Thechangeo fi r onc ompo s i t i ona swe l la st her emova lo fc oppe rf r omi r onwa si nve s t i t edi nt her educ t i on ga r o c e s s,andanew wayt ode a lwi t hc oppe rs l agwa sp r opo s ed．Thei r oni nc oppe rs l agex i s t sma i n l nt hef o rmo f p yi f aya l i t e,andt hec oppe rsu l f i dec on t en ta c c oun t sf o rj us tabou t５０％．The r e f o r e,t hemagne t i cs epa r a t i ona swe l la s r i nd i ngf l oa t a t i onme t hodi sno tsu i t ab l e,andapy r ogen i ct r e a tmen tonc oppe rs l agi sne c e s s a r a r bu r i z a t i on g y．Thec andde su l f u r i z a t i onp r o c e s si sr e s t r i c t edt oadeg r e ewi t h i nt hec a r bonc ompo s i t epe l l e t s,andc oppe rma t t epha s ep r e Ｇ c i i t a t e sf r omc oppe rs l agi nt her educ t i onp r o c e s s,wh i chi simmi s c i b l ewi t h mo l t eni r onands l ag．Thec oppe rc on Ｇ p t en tde c r e a s e st o０ ４％ a st hec a r bonc on t en ti n mo l t eni r onr e a che s３ ８４％ ,andt her emova lr a t i oo fc oppe rf r om mo l t eni r onapp r oa che st o８０％．Ther educ t i onandsu l f u r i z a t i onp r o c e s sc anbec omp l e t edi nones t ep,andt hec oppe r i ss epa r a t edf r omi r onba s edont het e r na r s t emo fi r on Ｇma t t e Ｇ s l ag． ysy Ke r d s:c oppe rs l ag;r educ t i on;su l f u r i z a t i on;ma t t e ywo
Py r ome t a l l u r st he mo s timpo r t an tp r o c e s s gyi f o rc oppe rsme l t i ngcu r r en t l heou t tby wh i ch y,t pu [] a c c oun t sf o r８０％ o ft het o t a l,even９７％i nCh i na１ ． They i e l do fc oppe rs l agi s２ ２tpe rt onc oppe r, i r on a swe l la scoppe rc on t en t so fwh i cha r e３０％ －４０％ [ ２] and０ ５％ －２ ０％ ,r e spe c t i ve l r e f o r e,s i Ｇ y ．The g n i f i c an te conomi cbene f i t s wi l lbea c i r edv i at he qu r e c l eo fcoppe rs l ag． yc Thewaysf o rc oppe rs l agu t i l i z a t i oni nc l udef i r e d i l u t i on and g r i nd i ng f l oa t a t i on．Thef i r ed i l u t i on me t hodl owe r st hec oppe rd i s s o l u t i onc on t en ti ns l ag v i ar educ t i onandsu l f i d i z a t i on,andc oppe ri sr e c ov Ｇ [ ３ Ｇ ６] , e r edi nt hef o rmo fsu l f i de s t hey i e l do fwh i chi s [] r e l a t i ve l ow ４ ．Theg r i nd i ngf l oa t a t i ont e chno l ogy yl [ ] i sma i n l i c a lt r e a tmen tp r o c e s s７Ｇ１１ ,wh i chi s yaphys us e f u lf o rr e c l eo fme t a l l i cc oppe randc oppe rsu l Ｇ yc f i de pha s e s,bu ti nc apab l eo f ox i de s．The r e f o r e,
cu l t,bo t ho fwh i cha r ecomp l e t e l s c i b l e．Hue t y mi [ ] a l １２ i nve s t i t edt hef e a s i b i l i t fcoppe ri nCu２OＧ ga yo FeO s t em wi t h CaCl２ ,andt her emova lr a t eo f ys coppe rr e a ched５５ ５％ whenhe l da t１０００ ℃f o r４h． Mo r eove r,t he coppe rr emova lr a t er e a ched ７０％ wh i l ehe l da t１０００ ℃ f o r１５ mi n,whenFeOＧS iO２Ｇ [ [ ] １３] CaCl２ compoundf l ux wa sus ed ．Wange ta l １４ s t ud i edt heequ i l i br i um o f Fe ＧS ＧC s t em;i t wa s ys f oundt ha tCandS we r eexc l us i vet oe a cho t he ri n mo l t eni r on,anda mi s c i b l e gapf o rmed whent he c a rboncon t en ti ni r onwa sh i r eove r, ghenough．Mo
t hee f f e c to fa l ka l i neo ra l ka l i nee a r t hsu l f i de son [ ] １５, coppe rr emova lf r om mo l t eni r on wa ss t ud i ed １６ , wh i chenhanc edt hed i s t r i bu t i onr a t i oo fc opp e rb e Ｇ [ ] twe e nma t t eand mo l t e ni r on．Be s i d e s,Longe ta l １７ r epa r edt heMo ＧFea l l oyf r omcoppe rs l agt hr ougha p two Ｇ s t ep me t hod,and coppe r wa sr emovedf r om mo l t eni r oni nt hef o rmo fcoppe rsu l f i de s,wi t had Ｇ bo t hf i r ed i l u t i onand g r i nd i ngf l oa t a t i ont e chno l o Ｇ ; , i t i ono fFeS ＧNa２Sf l ux f i na l l hecoppe rcon t en t yt i e sa r es e l e c t i vet ot he mo r l ogy o f mi ne r a l s． d g pho [ ] ni r ond e c r e a s e dt o０ １％． I na dd i t i on,Yama c h i１８ Mo s timpo r t an t l hei r oni sno tr e c l edv i at he i gu y,t yc t ud i e dt hec opp e rr emov a lf r om c a r bons a t u r a t e di r on two ways, wh i chi ss t i l li ns l ag．The r e f o r e,t he s , me l twi t hanox i da t i on me t hod wh i chadop t ed Ag t ho r oughr educ t i ono fc oppe rs l agi sne c e s s a r y． smed i um pha s eandB２O３ a spa r en tpha s e． Thes epa r a t i ono fc oppe rf r omi r onme l ti sd i f f i Ｇ a Founda t i onI t em: I t em Spons o r edbyNa t i ona lNa t ur a lSc i enc eFounda t i ono fCh i na ( ５１４０４０７５) B i o r aphy: JunZHANG,Do c t o r; E Ｇma i l: z x t ４２４＠１６３ c om Re c e i v e dDa t e:Do c embe r１６,２０１３ j g
I s sue５ A New Te chno l ogyf o rCoppe rS l agReduc t i ont oGe tMo l t enI r onandCoppe rMa t t e
３９７
I nt hep r e s en two rk,t hec oppe rs l ag wa sr e Ｇ duc edi nt hef o rm o fc a rbonc ompo s i t epe l l e t s,and mo l t eni r ona swe l la sc oppe rma t t ewa sa c i r edi n qu one Ｇ s t ep．Thus,t her emova lo fc oppe rf r om i r on wa sr e a l i z edi nt her educ t i onp r o c e s s． F i na l l y,anew t e chno l ogyf o rc oppe rs l agr e c l eba s edont het e r Ｇ yc na r t emo fi r on Ｇma t t e Ｇ s l ag wa sp r opo s ed． ys ys
l l e t swe r el oadedi naco rundumd i s cwi t had i ame Ｇ pe t e ro f５０mm,wh i chwa st henhe l da t１１００and１３５０ ℃f o r３０ mi n,r e s e c t i v e l i n a l l hes amp l e wa s p y．F y,t d r awnou to ft het ubeandcoo l eddowni na i ra tt he endo ft hehe a t i ng s t age．Thecompos i t i ono fi r on nugge t swa sde t e rmi nedt hr ought hechemi c a lt i t r a Ｇ t i onana l i s,andt hei r ony i e l do fs amp l e swa sde Ｇ ys t e rmi neda sf o l l ows． １ Exp e r imen t a l m ( η＝ ×１００％ １) m０ １ １ Ma t e r i a l s r e,ηi st hei r ony i e l d,％ ;m i st hema s so fi r on Thecompo s i t i onso ft hec oppe rs l agandc oa l whe , ; t g andm０i st hema s so ft o t a li r oni ns amＧ us eda r eg i veni nTab l e s１and２,r e spe c t i ve l y,and nugge l e,g． t he i rpa r t i c l es i z ei sbe twe en０ ０７４and０ １５０ mm． p Be s i de s,pur echemi c a lr e agen t so fr educ edi r onand ４ S e r a t i onbe twe enc oppe randmo l t eni r on r aph i t epowde rwe r ei nvo l vedi nt hep r e s en two rk． １ pa g Theg r aph i t ec ruc i b l el oadedwi t hs amp l e swa s Thei ng r ed i en t sa c c o r d i ng t or equ i r ed r a t i o s , l da t１３５０ ℃f o r１０－４０mi nd i r e c t l rN２a t Ｇ yunde we r e we i i ng an e l e c t r on i c ba l anc e wh i ch he ghed us mosphe r e,andt hec a rbonandcoppe rcon t en t swe r e we r et henmi xedandpr e s s edi n t oc l i nd r i c a ls amp l e s y t e rmi ned by chemi c a lt i t r a t i onana l i s;f i na l l ys y, wi t hama s so f９ ０gandxC/xO o f１ ５．Thes amp l e s de
we r ed r i edi nane l e c t r i cb l a s td r i ngovena t２００ ℃ y f o r６０ mi n． Tab l e１ Ch emi c a lc ompo s i t i ono ft h ec opp e rs l a s s％ g ma TFe
Cu
S
FeO
４０ ５７ ０ ７５ ０ ７８ ４２ ７４
S iO２
CaO
３２ ７６ ３ ８４
MgO
１ ０４
Al２O３ ３ ８７
Tab l e２ Pr ox ima t eana l s i so fc o a l ma s s％ y Mo i s t ur e ０ ８６
Vo l a t i l e ５ ６２
Ash
１９ ８４
F i xedc a r bon ７３ ６８
１ ２ Chemi c a l pha s e sand mi c r o s c op i cana l s i so f y c oppe rs l a g Thechemi c a lpha s e so fc oppe rs l ag we r ede t e r Ｇ mi nedv i at hel e a ch i ngandchemi c a lt i t r a t i onana l Ｇ y s i s me t hod．Thepa r t i c l e so fc oppe rs l ag we r ec onＧ s o l i da t edbye e s i nw i t hqu a d r o la sc u r i nga e n ti n poxyr g amo l d,wh i ch wa smadei n t oanop t i c a ls l i c eonan e l e c t r i crubb i ng and po l i sh i ng ma ch i ne．The s l i c e , wa sobs e r vedbys c ann i nge l e c t r onmi c r o s c opy wi t h a magn i f i c a t i ont ime so f２０００i nt heba cks c a t t e r ed t t e rn,andt he mi c r o Ｇ a r e ac ompo s i t i onana l i so f pa ys s amp l ewa sc onduc t edt hr oughaspe c t r ome t e rc on Ｇ ne c t edt oi t． １ ３ Re du c t i on and sme l t i ng Ｇ s e r a t i on o fc oppe r pa s l a t h i nc a r bonc ompo s i t epe l l e t s gwi Ther educ t i onandsme l t i ng Ｇ s epa r a t i ono fc op Ｇ rs l agwa sc onduc t edi nadoub l e Ｇ t empe r a t u r ez one pe r e s i s t anc ef u rna c e unde r N２ a tmo sphe r e．The d r y
t her a t i oo fcoppe rr emova lf r omi r onnugge twa sde Ｇ f i neda sf o l l ows． CCu ( rCu＝１００－w TFe ０ /１００ ２) CCu st her a t i oo fcoppe rr emova lf r omi r on, whe r e,rCui ％ ;w TFei st o t a li r oncon t en to ft heo r i i n a l s a m l e, g p ０ ; ％ CCui st hecoppe rcon t en ti nt heo r i i na ls amp l e, g st hecoppe rcon t en ti ni r onnugge t,％． ％ ;andCCui
２ Re s u l t s
２ １ Ch emi c a lpha s e sa ndmi c r o s t r u c t u r eo fc o e rs l a pp g Thechemi c a lpha s ecompos i t i ono fCuandFeo f coppe rs l agi sg i veni nTab l e３． I tc anbes e ent ha t, t hei r on ma i n l i s t si nt hef o rm o ff aya l i t e,and yex t heamoun to fFeandFe３O４i ssma l l． I tme anst ha t t her e c l eo fi r onf r om coppe rs l ag v i a magne t i c yc s epa r a t i onme t hodi sno tapp l i c ab l e． Tab l e３ Ch emi c a lpha s eana l s i so fc opp e rs l a y g ％
I r on Ｇ be a r i ngpha s e
Coppe r Ｇ be a r i ngpha s e
iO２＋FeS ２FeOS
９２ ０５
Fe
０ ６４
Fe３O４
CuSO４
７ ２８ ８ ９２
Cu２O
３９ ９０
Cu
０ ７６
Cu２S
５０ ４２
Themi c r o Ｇmo r l ogyo fcoppe rs l agv i aSEM pho , obs e r va t i oni sg i veni nF i １ a n dr e l e v a n t c h emi c a l g compos i t i ono fs e l e c t ed pha s e s wa sde t e rmi ned by spe c t rum ana l i s,t her e su l to f wh i chi sg i veni n ys Tab l e４． I tc anbes e ent ha t,t hec opp e rma t t ep a r t i c l e
J ou r na lo fI r onandS t e e lRe s e a r ch,I n t e r na t i ona l Vo l ２２
３９８
i swr appeda r oundbyt heg l a s s s e,andt hepa r Ｇ ypha t i c l es i z ei ssosma l l( abou t６０μm)t ha tah i hr e g Ｇ i r emen tong r i nd i ngs i z ei sdemandedwheng r i nd Ｇ qu i ngf l oa t a t i onp r oc e s si sadop t ed．Mo r eove r,t hecop Ｇ rsu l f i de sa c coun tf o rj us tabou taha l fa c co rd i ngt o pe , Tab l e３．Tha ti s t her e cove r a t eo fcoppe rv i a yr r i nd i ngf l oa t a t i oni sno mo r et han５０％．I no t he r g wo rds,t heg r i nd i ngf l oa t a t i onp r oc e s si sno tagood cho i c ef o rcoppe rr e c l e． yc ２ ２ Re du c t i on and sme l t i ng Ｇ s e r a t i on o fc oppe r pa s l a t h i nc a r bonc ompo s i t epe l l e t s gwi Theg r a so fs amp l e sa f t e rr educ t i onandsme l t Ｇ ph
F i １ SEMima eo fc opp e rs l a g g g
Tab l e４ Sp e c t r umana l s i so fpo i n t s１and２i nF i １ ma s s％ y g
Po i n t
Po i n t１ Po i n t２
Ra t i o
S
Pb
Ma s sr a t i o
２０ ６４
１１ ８６
Ma s sr a t i o
０ ８０
３ ０２
Mo l a rr a t i o Mo l a rr a t i o
３５ ７６ ０ ７２
３ １８ ０ ４２
Fe
１７ １７
１７ ０７
３７ ９３
１９ ５１
Cu
５０ ３３
４３ ９９
O
Mg
Al
S i
K
Ca
Zn
２８ ５２
１ ２６
２ ５７
１９ ８１
０ ８０
２ ４４
２ ３１
５１ ２０
１ ４９
２ ７４
１９ ８１
０ ５８
１ ７５
１ ０１
i ng Ｇ s epa r a t i ona r eshowni nF i ２．I tc an bes e en pe a r si nt her educ t i onp r oc e s s． g , t ha tt he r ei sr edpowde r sp r e c i i t a t edf r om c oppe r The mi n e r a lc ompo s i t i ono ft her e dpowd e r swa s p s l agi nt her educ t i onpr o c e s s． de t e rmi ned by XＧ r ay d i f f r a c t i on (XRD)ana l i s, ys Theave r agec a rbonandc oppe rc on t en t so ft he andt her e su l ti sg i veni nF i ３．Hema t i t ewa sde t e r Ｇ g , , r edpowde rmi x t u r ewe r e６４ ５％ and０ ３％ r e spe c Ｇ mi nedi nt hepowde r s wh i chexp l a i nedt heco l o ro f t i ve l ti s,t hec oppe rc on t en ti sapp r ox ima t e l r s,andal i t t l eFeandCuO we r ea l sof ound． y．Tha y powde ０ ８５％i ft hec a rboni sexc l uded．The r e f o r e,anew Mo r eove r,ani so l ogue mi ne r a lo fA,wh i ch maybe , , , s ed i f f e r en tf r om t he mo l t ens l ag andi r onap Ｇ i nc l ude sFe３O４ MgFe２O４ CoFe２O４ Cu１２Mn１８O４ pha
( a)R ＝０ ３; ( b)R ＝０ ５; ( c)R ＝０ ８; ( d)R ＝１ ０．
F i ２ Ef f e c to fba s i c i t l t i ng Ｇ s epa r a t i onp r o c e s so fc opp e rs l a g yR onsme g
F i ３ XRDpa t t e rno ft h er e dpowd e r s g
andCuMn２O４ ,e t c ,wa sf ound．The s eox i de scou l d , no tex i s ti nt her educ t i onp r oc e s s wh i chmos tl i ke l y f o rmeda tt hecoo l i ngs t agei nt hea i r．The r e f o r e,i t c anbet hough tt ha tt her ed powde r sa r econve r t ed f r omt hema t t epha s e． Thee f f e c to fba s i c i t l f urandc a rboncon Ｇ yonsu t en t so fi r onnugge ti sshowni nF i ４． I t c a nb e s e e n g t ha t,t hesu l f urcon t en ti ni r onde c r e a s e s wi t hi n Ｇ c r e a s i ngba s i c i t fs amp l e,bu tt het r endi sno tob Ｇ yo v i ouswheni ti sbeyond０ ５．The r e f o r e,t her emova l o fsu l f urf romi ronnugge tv i af l uxi sr e s t r i c t edt oa
I s sue５ A New Te chno l ogyf o rCoppe rS l agReduc t i ont oGe tMo l t enI r onandCoppe rMa t t e
３９９
F i ５ Re l a t i on s h i e twe enc a r bonandc opp e r g pb c on t en t si ni r onnug e t g
F i ４ Ef f e c to fba s i c i t u l f u randc a r bon g yons c on t en t si ni r onnug e t g
deg r e e．Thec a rbonc on t e n ti sa lmo s tno ti n f l u e n c e dby , ba s i c i t w h i c hi sa r o u n d１ ２％． y
t i b l ei nt hei r on．
２ ３ Co e rr emo v a lf r ommo l t e ni r o ni nr e d u c t i o np r o c e s s pp Thechangeo fc a rbonandi r onc on t en t si ni r on wi t hho l d i ngt imei nt heg r aph i t ec ruc i b l ei sshown i nF i ５,whe r et heba s i c i t fs amp l e swa s１ ０． I t g yo c anbes e ent ha t,t hec a rbonc on t en ti nc r e a s e swi t h i nc r e a s i ngho l d i ngt ime,bu tt het r endf o rc oppe ri s i nve r s e,t hel owe s tc on t en to f wh i chi sj us tabou t , ０ ４％．Tha ti st hecoppe randc a rbona r ei ncompa Ｇ
３ １ Re du c t i ono fc oppe rs l a g Ther educ t i onr e a c t i onsi nvo l vedi ncoppe rs l ag a r el i s t edi nTab l e５． I tc anbes e ent ha tt hemi ne r a l s o fcoppe randi r ona r ee a s i l educ eda tasme l t i ng Ｇ yr r educ t i ont empe r a t ur e,wh i cht r ans f o rmi n t ome t a l Ｇ l i c pha s e s unde rr educ t i on cond i t i ons．The r e f o r e, t her educ t i ono fcoppe rs l agi st ho r oughno ma t t e r wha tk i ndo fmi n e r a l si sr e du c e d,wh i c he l imi n a t e st he
３ Di s c u s s i on
Tab l e５ Re du c t i onands u l f u r i z a t i onr e a c t i on si nc opp e rs l a g Re a c t i on
ΔGθ
/K Gene r a t i ngt empe r a t ur e
ΔGθ＝５７５４０－１６１T
３５７
CuSO４＋２C＝Cu＋２CO＋SO２
ΔG ＝６６９８２－３５４T
Fe３O４＋４C＝３Fe＋４CO ２FeOS iO２＋２CaO＋２C＝２Fe＋２CO＋２CaOS iO２
ΔGθ＝６５４８９９－６５９T
ΔGθ＝２０９７１１－３２５T
FeS＋CaO＋C＝Fe＋CO＋CaS
ΔGθ＝１４１３１０－１５４T
Cu２O＋C＝２Cu＋CO
Cu２S＋CaO＋C＝２Cu＋CO＋CaS
θ
ΔGθ＝１１６４７８－１２５T
４５１ ９９４ ６４５ ９３２ ９１８
１ ６％ whent he ba s i c i t s beyond ０ ５．Tha ti s, yi t he r ei snof ur t he rde su l f ur i z a t i ont hr oughs l agwhen ３ ２ Ca r bu r i z a t i onandd e s u l f u r i z a t i oni nr e du c t i on t hec a rboncon t en ti ni r oni sl ow,andaf ur t he rde Ｇ r o c e s s c r e a s eo fs u l f u rc o n t e n t m u s tb ee s t a b l i s h e do nt h e p I ti sknownf r om above Ｇmen t i onedr e su l t st ha t ba s i so fh i rc a rbur i z a t i oncon t en t．Thede su l f u Ｇ ghe i z a t i onp r oc e s so f mo l t eni r onc anbede s c r i beda s t he c a rbon c on t en to fi r on nugge ti sj us t abou t r １ ２％ ,a l t houghc oa li si nexc e s s． I tme anst ha tt he f o l l ows: ( Fe]＋ [ S]⇔ [ FeS] ３) c a rbu r i z a t i onp r o c e s si nt hec a rbonc ompo s i t epe l l e t [ FeS]＋ ( CaO)＋ [ C]＝ [ Fe]＋ ( CaS)＋CO ( ４) i sr e s t r i c t edt oac e r t a i ndeg r e e,wh i chha sbe end i s Ｇ [ [ ] cus s edi ne a r l i e rwo rk１９ ．Howeve r,t hec a rbonc on Ｇ Ther e a c t i on ( ３)move st owa rdt her i h td i r e c t i o n g , t en tc anr e a chah i l uei nt heg r aph i t ec ruc i b l e． whent hec a rboncon t en ti nc r e a s e s duet ot her epu l Ｇ ghva The r e f o r e,t hec a rbons a t u r a t i onc ond i t i onc anno tbe s i onbe twe enc a rbonandsu l f ur,andt hent hede su l Ｇ r e a l i z ed wi t h i nt he c a rbon c ompo s i t e pe l l e t s,and f ur i z a t i onp r oc e s soc cur sv i as l agi nt hef o rmo fr e a c Ｇ ( ) s omeme a sur e se l s emus tbet aken． t i on ４ ．Ast hec a rboncon t en tde c r e a s e st oac e r t a i n Thesu l f u rc on t en ti ni r oni si n f l uenc edbyt he deg r e e,t her e a c t i on ( ３)i sr e s t r i c t ed,andr e a c t i on ba s i c i t fs amp l e s;howe v e r,i ti sac on s t a n to fa bou t ( ４)c e a s e s． I tc anbet hough tt ha tt hede su l f ur i z a t i on yo r e s t r i c t i ononc ompo s i t i ono fc oppe rs l ag．
４００
J ou r na lo fI r onandS t e e lRe s e a r ch,I n t e r na t i ona l Vo l ２２
r o c e s soc cur sbe twe ent hepha s e so fs l agandma t t e． p Mo r eove r,t hef o rma t i ono fCu２Si sont heba s i so f FeSex i s t enc e． ( [ FeS]＋２[ Cu]＝ [ Fe]＋ [ Cu２S] ５) The r e f o r e,how t oc on t r o lt her educ t i ondeg r e eo f , FeSi sc r i t i c a l wh i chi sr e a l i z edbyad us t i ngt heba Ｇ j s i c i t fs l aga c c o r d i ngt or e a c t i on ( ４)． yo ３ ３ Coppe rr emo v a lf r om mo l t e ni r on Ther e l a t i onsh i twe enc a rbonc on t en tand p be c oppe rr emova lr a t ei sshowni nF i ６． I tc anbes e en g t ha tt her emova lr a t eo fc oppe rf r omi r oni nc r e a s e s wi t hi nc r e a s i ngt hec a rbonc on t en t,wh i chi sc l o s et o ８０％ whent hec a rbonc on t en ti s３ ８４％．
ob t a i nedi nones t ep．Ba s edont h i s,anewt e chno l o Ｇ t od e a lw i t hc o e rs l a a sd e i c t e di n F i ７i s gy pp g p g r opos ed．Thecoppe rs l a t hR ＝１ ０andxC/xO ＝ p gwi １ ５i sr educ edandsu l f ur i z edbyt hecoa li nc a rbon , compos i t epe l l e t sf i r s t l a n dt h e nt h es m e l t i n Ｇ ep Ｇ y gs a r a t i onp r oc e s si scomp l e t eda t１３５０ ℃i nasme l t e r f urna c e wi t hacokel aye r,wh i chi si n t r oduc eda s c a rbur i z i ngagen tt ome e tt hec a rbons a t ur a t i oncon Ｇ , d i t i oni n mo l t eni r on．F i na l l he mo l t eni r on wi t h y t coppe rcon t en tl owe rt han０ ４％ andc a rboncon t en t , c l os et o４％ i sob t a i ned andt hecoppe ry i e l dv i a ma t t eapp r oa che st o８０％．
F i ７ S ch ema t i cd i a r amf o rc opp e rmi n e r a lt r e a tmen t g g
４ Conc l u s i on s
F i ６ Ef f e c to fc a r bonc on t en tonc opp e rr emo v a l g
Almo s ta l lt h ec opp e rd i s s o l v e si nt h emo l t e ni r on wh e nt hes u l f u rc on t e n ti ni r oni sh i hec a rbon gh．Ast c on t en ti nc r e a s e s,t hec oppe ri nt hei r ont r ans f o rms i n t oma t t epha s eduet ot hei nc ompa t i b i l i t twe en ybe CandSi ni r on． F i na l l hec oppe ri sr emovedf r om y,t i r on．Thecoppe ri sr emovedf r om mo l t eni r oni nt he f o rmo fCu２S,noma t t e rwha tt hek i ndo ft heex i s t Ｇ enc ef o rm o fc oppe ri si nr aw ma t e r i a l s,wh i chen Ｇ su r e st heh i e c ove r a t eo fc oppe r． ghr yr
( １)Thei r oni nc opp e rs l a x i s t sma i n l nt he ge yi f o rmo ff aya l i t e,wh i chme anst ha tt hemagne t i cs ep Ｇ a r a t i oni sno tapp l i c ab l e．Thecoppe rsu l f i decon t en t , o ft hecoppe rs l agi sj us tabou t５０％ andt hecoppe r ma t t epa r t i c l e sa r esma l landwr appedbyt heg l a s s y s e．The r e f o r e,t he e f f e c to f coppe rr e cove r pha y , t hr ought heg r i nd i ngf l oa t a t i onme t hodi swe ak and t hepy r ogen i ct r e a tmen toncoppe rs l agi sne c e s s a r y． ( ２)Thec a r bu r i z a t i onc on t e n to fi r oni sr e s t r i c t e d , wi t h i nt hec a r bonc ompo s i t ep e l l e t s wh i c hi sj u s tabou t １ ２％ ,andt hesu l f urcon t en ti ni r on ma i n t a i nsa t １ ６％ whenba s i c i t sove r０ ５．Mo r eove r,t he r ei s yi ama t t epha s ebe a r i ngcoppe rp r e c i i t a t edf r om s l ag p i nt her educ t i on p r oc e s s,wh i chi simmi s c i b l e wi t h mo l t eni r onands l ag． ( ３)Thec opp e rc on t e n td e c r e a s e st o０ ４％ a st he c a rboncon t en ti n mo l t eni r onr e a che s３ ８４％ ,and t her emova lr a t i oo fcoppe rf r om mo l t eni r oni sc l os e , t o８０％ wh i chensur e sah i e cove r a t i oo fcop Ｇ ghr yr r．Be s i de s,t he de su l f ur i z a t i on o fi r oni s de t e r Ｇ pe mi nedbyt hec a rboncon t en twi t h i ni t,andt her e Ｇ duc t i ono fsu l f i de si supt ot heequ i l i br i um be twe en t hema t t eands l agpha s e s． ( ４)Anewp r oc e s st ode a lwi t hcoppe rs l agand conc en t r a t e s,wh i ch wa sba s edont het e rna r Ｇ ys ys , t emo fi r on Ｇma t t e Ｇ s l ag wa sp r opos ed．Ther educ t i on
３ ４ Pr opo s a lo fanewwa o rc oppe rs l a e c c l e yf gr y Di f f e r en tk i ndso fi r onandc oppe rmi ne r a l sd i s Ｇ t r i bu t eamongs l ag,ma t t eandi r onpha s e s,r e spe c Ｇ t i ve l t t e r wha tt hek i ndo fc oppe rs l agi s． y,no ma The r e f o r e,t hepr o c e s so fr educ t i onandsu l f u r i z a t i on i sj us tame anst ot r ans f e rt hemamongt he s epha s e s． The r ea r etwof a c t o r sf o rt hes epa r a t i ono fc oppe r f r omi r on:onei st hec a rbonc on t en to fi r on,andt he o t he ri st heex i s t enc eo fc oppe ri nt hef o rmo fCu２S． Thec a rbu r i z a t i onandsu l f u r i z a t i onc anbec omＧ , l e t eds imu l t aneous l nt her educ t i onp r o c e s s wi t h p yi noadd i t i ono fsu l f u r i z i ngr e agen t,andt hei r ona l l oy andsu l f ur i z a t i on p r oc e s si scomp l e t edi n ones t ep t h i nt hec a rboncompos i t epe l l e t s,andf ur t he rc a r Ｇ wi t hl owcoppe rc on t en ta swe l la sc oppe r ma t t ei s wi
I s sue５ A New Te chno l ogyf o rCoppe rS l agReduc t i ont oGe tMo l t enI r onandCoppe rMa t t e
bu r i z a t i on pr o c e edsi nt hesme l t e rf u rna c e wi t ha , c okel aye r． F i na l l t h em o l t e n i r o nw i t hc o e r c Ｇ y pp on t en tl owe rt han０ ４％ andc a rbonc on t en tc l o s et o ４％i sob t a i ned,andt hec oppe ry i e l dv i a ma t t eap Ｇ , r o a c h e s t o８ ０％ w h e nt h es a m l eo f R ＝１ ０a n d p p xC/xO ＝１ ５i she l da t１３５０ ℃． Re f e r enc e s: [ １] B．L i,H．Wang,J H．Hu,L．L i,Mi n i ngand Me t a l l ur gy１８ ( ２００９)No １,４４ Ｇ ４８． [ ２] J H．Hu,H．Wang,HL．L i u,L．L i,J our na lo fHunan Un i Ｇ ve r s i t fSc i enc eand Te chno l ogy,Na t ur a lSc i enc eEd i t i on２６ yo ( ２０１１)No ２,９７ Ｇ １００． [ ３] L N．Zhang,L．Zhang,MY．Wang,Z D．Su i,Non f e r r ous Me t a l s５７ ( ２００５)No ３,４４ Ｇ ４７． [ ４] HQ．Chen,P X．L i,S G．L i u,Z J． Zhang,HuNanNon f e r Ｇ r ousMe t a l s２２ ( ２００６)No ３,１６ Ｇ １８． [ ５] R G． Re ddy,V L． Pr a bhu,D．Ma n t h a,Mi n e r．Me t a l l． Pr o c e s s． ２３ ( ２００６)９７ Ｇ １０３． [ ６] S．Va i s bu r d,D G．Br a ndon,S．Ko z h akhme t o v,E．Ke n z h a l i e v, y Me t a l l．Ma t e r．Tr ans．B３３ ( ２００２)５６１ Ｇ ５６４．
４０１
[ ７] A． Sa r r a f i,B．Rahma t i,HR．Ha s s an i,HHA． Sh i r a z i,Mi n Ｇ e r．Eng． １７ ( ２００４)４５７ Ｇ ４５９． [ ８] WJ．Br u c k a r d,M．Some r v i l l e,F．Ha o,Mi n e r．Eng．１７ ( ２００４)
４９５ Ｇ ５０４． [ ９] R． J i n,J S．Wang,QR．Long,J i angx iNon f e r r ous Me t a l s２３ ( ２００９)No １,１２ Ｇ １４． [ １０] MA．We i,Mi n i ngand Me t a l l ur ２００４)No １,３８ Ｇ ４１． gy１３ ( [ １１] J A．Chen,E M．Gong,X B．L i,J．L i u,J our na lo fJ i angx i Un i ve r s i t fSc i enc eandTe chno l ogy３１ ( ２０１０)No ３,１９ Ｇ ２１． yo [ １２] X J．Hu,P G．J i ang,Z．Yan,L Q．Zhu,KC．Chou,H． Ma t suur a,F．Tsuk i ha sh i,I S I JI n t． ５３ ( ２０１３)５４１ Ｇ ５４３． [ １３] X J．Hu,Z．Yan,P G． J i ang,L Q． Zhu,K．Chou,H．Ma t Ｇ suur a,F．Tsuk i ha sh i,I S I JI n t． ５３ ( ２０１３)９２０ Ｇ ９２２． [ １４] C．Wang,J．Hi r ama,T．Naga s aka,S．Ban Ｇ S I JI n t．３１ ya,I ( １９９１)１２９２ Ｇ １２９９． [ １５] C．Wang,T．Naga s aka, M．Hi no,S．Ban Ｇ S I JI n t．３１ ya,I ( １９９１)１３００ Ｇ １３０８． [ s aka, M．Hi no,S．Ban Ｇ S I JI n t．３１ １６] C．Wang,T．Naga ya,I ( １９９１)１３０９ Ｇ １３１５． [ Pa l a c i o s,M． Sanche s,T．Mi k i,Y． Sa s ak i,M． １７] T V．Long,J． Hi no,I S I JI n t． ５２ ( ２０１２)１２１１ Ｇ １２１６． [ １８] K．Yamaguch i,H．Ono,I S I JI n t． ５２ ( ２０１２)１８ Ｇ ２５． [ １９] J． Zhang,YH．Qi,D L．Yan,X L．Cheng,P．He,J． I r on S t e e lRe s． I n t． ２２ ( ２０１５)１２１ Ｇ １２７．