SOLVENT EXTRACTION

PRINCIPLES, APPLICATIONS AND PROBLEMS EMPHASIS ON COPPER A SHORT COURSE CHILE MAY 8- 9, 20 0 3 Cours e Outlin e
Primarily, this Short Cours e on Solven t Extraction in Chile is direct e d to the Copp er indus try. There is a long history of copp e r recov e r y by solven t extr a c tion, dating back to the first SX E! Cu plant in "#$# in %ri&ona. Chile is no' one of the ma(or produc e r s of copp e r, ag ain using SX E!. %lthoug h the basic proce s sin g flo'sh e e t sho' s little chan g e in almos t )* years , and thoug h ores may be similar, the actu al plant practic e and slight differe n c e s in the design ma y result in differe n t proble m s being encou n t e r e d . Thus, the Cu SX proc e s s is no' 'ell kno'n, and consid e r e d by ma n y as eas y to design and to imple m e n t . +o'ev er, in the design of the actu al proce s s ther e are ma n y factors to be consid er e d if minimu m proble m s are to result in the subs e , u e n t oper a tio n. To optimi&e the design the cons tr ain t s to the dev elop m e n t hav e to be recog ni& e d early. Thes e 'ill includ e the nat ur e of the leach li,uor -anions , cations , orga nic impurities./ the solven t comp o sition -extr ac t a n t , diluent and possible modifier./ rat e of extr ac tio n -and stripping./ stag e s re,uir e d/ oper a tin g te m p e r a t u r e / the selection of the cont a c t o r and oper a tin g condition s as affecting mas s transf er and coale s c e n c e / the influenc e of the recycle stre a m s -from E! and 'at er reclai m pond.. 0ecau s e all of the abov e can hav e a ma(or impact on the solve n t loss e s in the plant -solubility, eva p o r a tio n, misting, degr a d a tio n , sta bl e emulsion s and cruds., it is instructiv e to learn, 'her e possible, the exp erie n c e s encou n t e r e d in oth er SX recov e r y plant s for other me t al s. This short cours e 'ill ther efor e focus on the abov e to provide the nec e s s a r y inform a tio n that might improv e existing copp er oper a tio n s , as 'ell as to indicat e to ne' pros p e c tiv e oper a tio n s the chan g e s in proc e s s and plant design s that could result in ma(or cost reduc tio n s .

1n addition to the cours e pres e n t a ti o n, ther e 'ill be som e plant proble m s pres e n t e d and discus sion s on the solution to thos e and other proble m s in the copp e r indus try. 2any proble m s enco u n t e r e d in the copp er indus tr y are not uni,u e to that indus tr y, and can be found in ma n y me t al s recov er y plant s. 0elo' is sho'n the Conte n t s of the SX Short Cours e, and altho u g h ,uite compr e h e n s iv e for a 3 day cours e, nev er t h el e s s mos t of the sub(ect are a s 'ill be discus s e d . 0eca u s e the sever al are a s of the solven t extr ac tio n proce s s are cover e d in det ail in Texts by the auth or -S456E7T EXT8%CT147 Principles and %pplications to Proces s 2etallurgy, 6ol "93. Pub. Elsevier Publisher s , %mst er d a m . and the fact that ma n y of the visual pres e n t a ti o n s repr e s e n t s the inform a tio n found in the Texts, then the Cours e 7otes are by nec e s sit y short.

ii

Ta l e o! Cont e n t s
SECTIO" I#############################################################################################################################################################$ THEORY A"% &RACTICE#################################################################################################################################$ T+E S456E7T EXT8%CT147 P84CESS........................................................................................................... " The Practical Process of Solvent Extraction.................................................................................................2 The Theory of Solvent Extraction..................................................................................................................3 Systems Involving Compound Formation...................................................................................................... !cidic Extractants.........................................................................................................................................." Systems Involving Ion !ssociation................................................................................................................" Systems Involving Solvation........................................................................................................................## S42E P8%CT1C%5 C47S1:E8%T147S........................................................................................................... "3 Extraction Coefficient $E%............................................................................................................................#2 Extractant Concentration............................................................................................................................#3 Effect of p&..................................................................................................................................................# !'ueous Phase Composition........................................................................................................................#( )etal Ion Concentration..............................................................................................................................#( Solvent *oading Capacity............................................................................................................................#( +inetics of Extraction..................................................................................................................................#, SECTIO" II##########################################################################################################################################################20 E'TRACTA"TS, %ILUE"TS, A"% MO%I(IERS########################################################################################2$ EXT8%CT%7T C5%SS1;1C%T147S.................................................................................................................. 3" !cidic Extractants........................................................................................................................................2# !l-ylphosphorus !cids.................................................................................................................................2# Car.oxylic !cids..........................................................................................................................................32 /asic Extractants.........................................................................................................................................33 0eutral Extractants......................................................................................................................................3" Chelating Extractants $!cidic Extractants%................................................................................................3" Solvents Containing )ixed Extractants...................................................................................................... # 1iluents........................................................................................................................................................ 2 S+E55S45 3<=$ %8 E6%P48%T147 8%TE.................................................................................................... == ................................................................................................................................................................. == ;1>?8E 3<@ E;;ECT 4; 7%T?8E 4; :15?E7T 47 T+E EXT8%CT147 4; 8%8E E%8T+S..................................=$ )odifiers......................................................................................................................................................(2 Summary.......................................................................................................................................................(3 SECTIO" III########################################################################################################################################################)* &ROCESS %ESI+"#############################################################################################################################################)* 17T84:?CT147.......................................................................................................................................... *= C+E21ST8A................................................................................................................................................ *= Extractants...................................................................................................................................................( )odifiers......................................................................................................................................................( 1iluents........................................................................................................................................................(( 2%SS T8%7S;E8 :1SPE8S147 %7: C4%5ESE7CE.........................................................................................** EB?1P2E7T................................................................................................................................................ $" EC47421CS............................................................................................................................................... $3 :ES1>7 4; T+E P84CESS............................................................................................................................ $) SECTIO" I,########################################################################################################################################################-. /E"CH TESTI"+ CO"TI"UOUS TESTI"+ &ILOT &LA"T &LA"T##############################################-. SC%5E ?P@ 0E7C+ C47T17?4?S T4 P154T P5%7T.......................................................................................$C /ench Continuous........................................................................................................................................,3 Pilot Plant....................................................................................................................................................,4 Plant.............................................................................................................................................................,"

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SECTIO" ,##########################################################################################################################################################.$ E0UI&ME"T#######################################################################################################################################################.$ SECTIO" ,I########################################################################################################################################################8) RECO,ERY O( CO&&ER#################################################################################################################################88E%>E7T :E6E54P2E7T............................................................................................................................ D$ EXT8%CT%7TEC%TE>48A........................................................................................................................... D# 8E%>E7T................................................................................................................................................... D# E%85A C4PPE8 4PE8%T147S...................................................................................................................... #" Sulphate Systems.........................................................................................................................................."# 0itric !cid Systems......................................................................................................................................"4 Chloride Systems.........................................................................................................................................."" !l-aline !mmonium Sulphate Systems......................................................................................................#2# 24:E87 4PE8%T147S.............................................................................................................................. "<# T4T%5 C+15E "$*< ........................................................................................................................... ""< 8E;E8E7CES............................................................................................................................................ ""3 33.8E%:ETT, :., %7: T4!7S47, 0., P8%CT1C%5 %SPECTS 4; C4PPE8 S456E7T EXT8%CT147;842 %C1:1C 5E%C+ 51B?48S, P8ESE7TE: %T %5T% "##C C4PPE8 +A:842ET%55?8>A;48?2, 4CT. 3< 3", "##C, PE8T+ %?ST8%51%................................................................................................................................... "") SECTIO" ,II#####################################################################################################################################################$$) P8405E2S E7C4?7TE8E: 17 C4PPE8 S456E7T EXT8%CT147 P5%7TS ...............................""* SECTIO" ,II####################################################################################################################################################$3$ &ROCESSI"+ O( COM&LE' /ASE METAL SUL&HI%ES#####################################################################$3$ 17T84:?CT147......................................................................................................................................... ")" P84CESS 4PT147S.................................................................................................................................... ")) Sulphate Processes.....................................................................................................................................#33 Chloride Processes.....................................................................................................................................#3( Solution Purification..................................................................................................................................# 2 #############################################################################################################################################################################$*3 SECTIO" ,III###################################################################################################################################################$** RECO,ERY O( URA"IUM###########################################################################################################################$** 17T84:?CT147......................................................................................................................................... "== EXT8%CT%7TS......................................................................................................................................... "=$ !cidic extractants......................................................................................................................................# , /asic extractants........................................................................................................................................# , 0eutral extractants.....................................................................................................................................# 3 24:1;1E8S............................................................................................................................................... "=D :15?E7TS................................................................................................................................................ "=D EXT8%CT147 2E:1%................................................................................................................................. "=# Sulphate Systems........................................................................................................................................# " 0itrate Systems...........................................................................................................................................#(" Chloride Systems........................................................................................................................................#,2 Solution )ining..........................................................................................................................................#,# 8E;E8E7CES............................................................................................................................................ "$3 SECTIO" I'######################################################################################################################################################$-SE&ARATIO" O( "IC1EL 2 CO/ALT######################################################################################################$-. P84CESS 4PT147S ?S17> S456E7T EXT8%CT147 ;48 T+E P84CESS17> 4; 5%TE81TES.............................."$C &istorical Co50i Separation .y Solvent Extraction..................................................................................#,3 6hy do 7e Choose Solvent Extraction8....................................................................................................#,4 Extractants for Co50i.................................................................................................................................#,4 1iluents......................................................................................................................................................#3(

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%PP51C%T147 4; SX T4 5%TE81TE 5E%C+ S45?T147S..............................................................................."C* Co50i Solvent Extraction Process Flo7sheets..........................................................................................#3, 9e:ection of Impurities...............................................................................................................................#34 Solvent Extraction Test Program...............................................................................................................#3" Considerations in 1esign...........................................................................................................................#42 Final Products............................................................................................................................................#42 4PE8%T147.............................................................................................................................................. "D" P84CESS %7: E7>17EE817> 1SS?ES.......................................................................................................... "D" 9elia.ility of Scale5;p...............................................................................................................................#4# Economics..................................................................................................................................................#42 C47C5?S147............................................................................................................................................ "D3 8E;E8E7CES............................................................................................................................................ "D) SECTIO" '########################################################################################################################################################$8RECO,ERY O( &RECIOUS METALS#########################################################################################################$8. SECTIO" 'I######################################################################################################################################################$92 SE&ARATIO" O( 3IRCO"IUM A"% HA("IUM#####################################################################################$93 +74 T0P SASTE2.................................................................................................................................. "#) 210F +C5 SASTE2................................................................................................................................ "#) 8E;E8E7CES............................................................................................................................................ "#$ SECTIO" 'II#####################################################################################################################################################$9. E",IRO"ME"TAL AS&ECTS######################################################################################################################$9. 17T84:?CT147......................................................................................................................................... "#C +A:84C%8047S...................................................................................................................................... "#C T4X1C1TA 4; S42E 8E%>E7TS T4 ;1S+.................................................................................................... "#D ECO"OMICS#####################################################################################################################################################203 SECTIO" 'I,####################################################################################################################################################20) (LO4SHEETS O( THE (UTURE################################################################################################################20) SECTIO" ',#####################################################################################################################################################2$$ S' &ROCESSI"+ &LA"TS - &RO/LEMS, ASSESSME"TS, SOLUTIO"S###########################################2$2 S42E P8405E2S :?E T4 S151C%.............................................................................................................. 3") P+AS1C%5 %SPECTS G E2?5S147 9 C8?:S...............................................................................................3"= Some Factors Causing Crud......................................................................................................................2# 2ET+4:454>A 4; C8?: P8E6E7T147..................................................................................................... 3"*

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SECTION I THEORY AND PRACTICE

The Solvent Extraction Process The proce s s of solven t extr a c tion -or li,uid li,uid extr ac tio n. is a sep a r a tio n tech ni, u e involving ma s s transf er acros s a phas e boun d a r y, and as such is not limited to met al transf er from an a,u e o u s to a non a,u e o u s phas e , or, vice vers a. !e shall her e, ho' ev e r, restrict ours elv e s to the application of the solven t extr ac tio n techni, u e to met allurgic al proce s sin g. 0asically, the proce s s of solven t extr a c tion as applied to met als sep a r a tio n and purification re,uir e s only that a specific me t al be transf err e d from, initially, an a,u e o u s phas e to a non a,u e o u s pha s e , follo'e d by a revers al of this transf er. Such a proc e s s can be define d simply by the follo'ing e,u a tio n@
2 H E 2E

-EB ".

+ere, and in subs e , u e n t e,u a tio n s , the non a,u e o u s phas e is deno t e d by a bar - . over the specie s consid e r e d to be pres e n t in that pha s e . E,uation " the n repr e s e n t s a situ a tion 'her e a met al specie s 2 in an a,u e o u s phas e is cont a c t e d 'ith a non a,u e o u s phas e cont aining extr a c t a n t E, 'her e b y a tran sf e r of met al 2 occurs acros s the phas e boun d a r y to prod uc e a species 2E 'hich is soluble in the non a,u e o u s phas e . This phe n o m e n o n is describ e d as extr ac tio n, and has as its ob(ectiv e the sep a r a tio n of a me t al G in this cas e 2 G from oth er me t al s or comp o n e n t s of an a,u e o u s syst e m . This proce s s of extr a c tion is an e,uilibriu m proc e s s , and the ext e n t to 'hich extr ac tio n occurs, i.e. to 'hich the e,uilibriu m is shifte d to the right in E,uation #, dep e n d s on sev er al factors, 'hich are discus s e d belo'. The extr a c tion proce s s thus provid e s met al tran sf e r from one pha s e to anot h e r. 1n me t allurgic al proce s sin g, a seco n d proc e s s is re,uire d in order to tran sf e r the me t al from the orga nic pha s e to a -ne'. a,u e o u s phas e . This, the stripping proce s s , is the rever s e of the extr a c tion proce s s , and re,uire s that the e,uilibriu m in E,uation " be shifted to the left. 1t is evide n t the n that the sep ar a tio n and recov er y of particular met al can, at leas t in theor y, be acco m plis h e d by t'o basic ma s s tran sf e r oper a tio n s involving t'o li,uid phas e s . ;or econo mic rea s o n s , the t'o phas e s involve d hav e minim al mut u al solubility. The basic solve n t extr ac tio n proc e s s is, in theory any' a y, a simple one, 'hich dep e n d s ess e n ti ally on shifting the che mic al e,uilibriu m position of

a t'o phas e syst e m , by 'hich me a n s eith er met al extr a c tion or stripping is achiev e d . 0ut as is usu ally the cas e, the application of a basically simple oper a tio n to real situa tio n s incre a s e s som e ' h a t in comple xity. 7evert h el e s s , the basic simplicity of the solven t extr a c tion proce s s is a particular attr a c tio n for its use in me t allurgic al proce s sin g. The Practical Process of Solvent Extraction %pplication of the basic conc e p t of solve n t extr ac tio n to me t allurgical proce s sin g re,uire s that the e,uilibriu m conditions discus s e d abov e be sep a r a t e d . This is achiev e d by conduc tin g the t'o basic re,uir e m e n t s of extr a c tion and stripping as sep a r a t e oper a tio n s . There ma y be one furth e r re,uire m e n t in the proce s s , na m ely an inter m e d i a t e purification of the me t al load e d non a,u e o u s pha s e prior to stripping the me t al from this phas e . This inter m e di a t e proce s s is called a scrub sta g e , and as for the oth er oper a tio n s , is nor m ally carrie d out as a sep ar a t e oper a tio n. % gen e r al solve n t extr a c tion circuit is sho'n sch e m a ti c ally in ;igure " . The me t al be aring a,u e o u s feed solution and solve n t are fed, usu ally in a count e r c u r r e n t ma n n e r , into a cont a c t o r in 'hich the t'o pha s e s are mixe d. 1n this extr a c tion stag e the met al of inter e s t is tran sf e rr e d from the a,u e o u s to the orga nic phas e . That is, the syst e m as repr e s e n t e d by E,uation " is so arra n g e d that the e,uilibriu m is shifted to the right. The mixtur e of a,u e o u s and orga nic li,uids flo's from the mixing sta g e to a settling sta g e in 'hich the t'o pha s e s sep a r a t e . The a,u e o u s phas e or raffinat e is remov e d and tre a t e d for the recov er y of other cont ain e d met als , is recycle d to som e point upstr e a m or do'ns tr e a m from the SX circuit, or goes to 'ast e . ;rom the extr a c tion stag e the orga nic phas e -load e d solve n t. no' cont ainin g the extr ac t e d me t al or met als ma y go to anot h e r cont a c t o r -scrub stag e . in 'hich it is cont a c t e d -scrub b e d . 'ith a suita ble a,u e o u s solution to remo v e un' a n t e d me t al s or impurities co extr a c t e d in the extr ac tio n stag e . %gain the a,u e o u s and solve n t phas e s are sep a r a t e d as before. The scrub raffinat e -a,u e o u s . may the n be recycle d to a sta g e upstr e a m from the SX circuits, for exa m pl e to the leaching sta g e , or to the a,u e o u s SX feed tank. The final stag e involves stripping the met al of inter e s t from the scrub b e d solven t. This re,uire s that the e,uilibriu m sho' n in E,uation " be shifted to the left, and this is acco m plis h e d by cont a c tin g the load e d solven t 'ith an a,u e o u s solution 'hich allo's this e,uilibriu m to shift. %gain, the mixe d pha s e s are sep a r a t e d , producin g -usu ally. a fairly conc e n t r a t e d a,u e o u s solution of the me t al salt and a met al free -ess e n ti ally. solven t phas e . 8ecycle of the stripp e d solven t to the first extr a c tion sta g e comple t e s the solve n t cycle. The a,u e o u s met al solution goes to furth e r proce s sin g for me t al produc tion. Each of the thre e stag e s describ e d G extr a c tion, scrub bin g and stripping G may involve sever al cont a c t o r s in each stag e . Thus the extr ac tio n of uraniu m from acid sulph a t e me di a using a tertiary amin e as the

extr a c t a n t may re,uir e thre e cont a c t o r s for extr a c tion, one for scrub bin g, and t'o for stripping.

(i5ur e $ The gen e r al proce s s of solve n t extr a c tion. The Theory of Solvent Extraction !hen a met al cont ainin g a,u e o u s phas e is shak e n 'ith an orga nic pha s e into 'hich the met al is extr a c t e d it 'ill be distribu t e d bet' e e n the t'o phas e s . The distribu tion may be che mic al or physic al in natur e , dep e n di n g on the syst e m . Physical proce s s e s are thos e involving the extr a c tion of simple, unch a r g e d co valent molecule s such as the halide s of ars e nic-111., anti mo n y-111., ger m a ni u m -111. and mercur y-11. into orga nic solven t s such as carbo n tetr a c hlorid e. Except for syst e m s similar to thos e note d abov e , che mic al reac tion s are involved in the extr a c tion of met als , and occur bet' e e n the met al specie s pres e n t in the a,u e o u s pha s e and one or mor e comp o n e n t s of the orga nic or solven t phas e . 7ormally a met al ion exists in a,u e o u s solution as a hydr a t e d ion, 'ith little or no tend e n c y to tran sf e r to an orga nic phas e . Thus in order to achiev e the re,uire d transf er the met al ion has to be modified in som e 'ay. To conv er t a met al ion to an extr a c t a bl e specie s its charg e neutr alis a tion and som e or all of its 'at er of to be replac e d by som e other molec ul e or ion. Thes e are the ma(or re,uire m e n t s and can be met by@ -i. compl exin g the me t al ion 'ith an ion of opposit e charg e to form a neutr al specie s 'hich, at the sa m e time replac e s som e or all of the 'ater of hydr a tion of the me t al ion/

-ii. -iii.

form a tio n of ion ass ocia tion comple x e s 'hich form a tio n of neutr al specie s 'ith an extr ac t a n t /

provide

for the

replacing the 'at er of hydr a tio n aroun d the met al ion 'ith solven t molec ul e s .

The over all proce s s is then one of conver tin g a hydrop hilic met al specie s into a hydro p h o bic specie s . The natur e of the extr a c t a bl e met al specie s is ther efor e of fund a m e n t a l import a n c e in me t al extr a c tion syst e m s , and it is logical to classify extr a c tion syst e m s on this basis. %ccordingly, the class e s of syst e m s consid er e d her e are@ -i. -ii. -iii. thos e 'hich involve comp o u n d form a tio n/ thos e 'hich involve ion ass ocia tion/ thos e 'hich involve salva tion of the met al ion.

This me t h o d of classification is but one of sever al/ it is not me a n t to imply that thes e syst e m s are mut u ally exclusive, but rath e r to simplify discus sio n s of the various syst e m s . 1nde e d, som e extr ac t a n t s can belong to more tha n one class, dep e n di n g in large me a s u r e on the proc e s s conditions . Systems Involving Compound Formation Such syst e m s includ e both chela tin g and acidic extr a c t a n t s - Table " .. ;or purpos e s of discus sing the basic prop er ti e s of thes e syst e m s , 'e shall conc er n ours elv e s 'ith chela tin g extr a c t a n t s . The simples t e,u a tio n 'e can 'rite to illustra t e the extr ac tio n of a me t al ion, 2n H , by an extr ac t a n t , +%, is 2 n H + n+ % 2% n + n+ H -EB 3.

'hich form ally res e m b l e s E,uation " and also the proc e s s of solid li,uid ion exch a n g e , in 'hich +% is e,uiv al e n t to an ion exch a n g e resin. 1t is not surprising, the n, that solven t extr ac tio n is also referr e d to as li,uid ion exch a n g e . Thus syst e m s employing chelating and acidic extr a c t a n t s are cation exch a n g e syst e m s , 'hile thos e employing amin e extr a c t a n t s are anion exch a n g e syst e m s . E,uation 3 sho's that the extr a c tion of a met al as describ e d by this e,u a tio n is heavily dep e n d e n t on the e,uilibriu m p+ of the a,u e o u s phas e , as indicat e d by the hydro g e n ion conc e n t r a ti o n, n+ H. Thus, as the p+ is decr e a s e d , -hydro g e n ion conc e n t r a ti o n incre a s e d . me t al extr a c tion 'ill decr e a s e since the e,uilibriu m 'ill be shifte d to' ar d s the

left. Convers ely, as the p+ is incre a s e d , -hydro g e n decr e a s e d . met al extr ac tio n 'ill incre a s e . 4f cours e, her e by the p+ at 'hich the met al hydrolys e s . The dep e n d e n t on the stability of the extr a c t a bl e met al 'hich is a function -in part. of the extr a c t a n t , but mor e

ion conc e n t r a ti o n a limit is impos e d extr ac tio n is also comple x form e d , of this later.

;or syst e m s 'her e the extr a c tion involves only very lo' met al conc e n t r a ti o n s , for exa m pl e trac er or pp m ,ua n tities as in an alytical che mis tr y, the amo u n t of hydrog e n ion forme d 'ill be small, and 'ill chan g e the e,uilibriu m p+ of the syst e m little. 4n the other hand, the extr a c tion of larg e amo u n t s of me t al, as in a com m e r ci al proc e s s , 'ill produc e corres p o n di n gly large amo u n t s of hydrog e n ion. ;or exa m pl e , in the extr a c tion of copp er by a mono b a s ic rea g e n t +%, the extr a c tion of one mol of copp e r 'ill produc e t'o mols of hydro g e n ion@ Cu S4 = + 3+ % Cu-%.3 + + 3 S4 = -EB ).

and in the extr ac tio n of ferric iron, thre e mols of hydro g e n ion 'ill be produc e d for every mol of ;e-111. extr a c t e d @ ;e 3 - S4 = . ) + $+ % 3;e-%. ) + )+ 3 S4 = -EB =.

1n order to achiev e high met al loading of the solven t the hydrog e n ion produc e d mus t ther efor e be neutr alis e d in som e 'ay, and exa m pl e s 'ill be given later as to ho' this is achiev e d . 7o' the degr e e to 'hich a me t al is extr ac t e d by an extr ac t a n t can be det er mi n e d simply by an analysis of the a,u e o u s phas e . Consid er the extr a c tion of copp e r as illustra t e d by E,uation *. 1f 'e shak e toge t h e r an a,u e o u s solution of copp er sulph a t e of kno'n conce n t r a ti o n 'ith a volum e of, say, a chlorofor m solution of D hydroxy ,uinoline -oxine. at a suita ble p+, the n at e,uilibriu m 'e 'ill hav e the condition@ Cu S4 = + 3+ 4x Cu-4x. 3 + + 3 S4 = -EB *.

The amo u n t of copp e r extr ac t e d is det e r mi n e d simply by analysis of the a,u e o u s phas e -raffinat e . after e,uilibriu m is achiev e d . Since the initial copp e r conce n t r a tio n is kno'n, the conce n t r a ti o n s of copp e r in the orga nic phas e -ass u mi n g no volu m e chan g e in the pha s e s occurs on shaking. can be calculat e d . Thus, und er the exp eri m e n t a l conditions use d , the ratio of copp e r in the t'o phas e s can be readily det er mi n e d , 'hich gives a good indication of the exte n t to 'hich the e,uilibriu m in E,uation * is shifte d to the right. The stat e m e n t abov e is und e rlin e d to emp h a s i& e that only und er the exp eri m e n t a l conditions use d 'ill the ratio of conce n t r a tio n s of met al be valid/ as 'e shall see later, eve n small chan g e s in exp e ri m e n t a l conditions can chan g e dra m a tic ally the res ult a n t ratio.

This analytic ally det e r mi n e d distribution of a met al bet' e e n an a,u e o u s phas e and an orga nic phas e is kno'n as the extraction coefficien t< design a t e d E, or the distri.ution coefficien t< : -'e shall use the form er her e., and is define d as@ EI concentration of m etal in the organic phase concentration of the m etal in the a,ueou s phase -EB $.

2etal conc e n t r a ti o n s are det er mi n e d an alytically, and are total conc e n t r a ti o n s of me t al, in 'hat e v e r form , in each phas e . This simple e,u a tio n for E is basic to all solve n t extr a c tion studie s , and provide s muc h of the dat a on 'hich solve n t extr ac tio n proc e s s e s are bas e d. %s define d, E is indep e n d e n t of the pha s e ratio of the a,u e o u s and orga nic pha s e s . +o'ev er, it should be evide n t that the pha s e ratio 'ill influenc e the amo u n t of met al extr ac t e d , since at a given conce n t r a ti o n of extr a c t a n t , -+%., the amo u n t of extr ac t a n t available for extr a c tion purpos e s is given by its conc e n t r a tio n multiplied by the phas e volum e @ Total amo u n t of +% I -+ %. v 'her e v is the volu m e of the orga nic phas e . 5et us no' look a little more clos ely at a solven t extr ac tio n syst e m involving comp o u n d forma tio n. The e,uilibriu m const a n t -F E. for the syst e m describ e d by E,uation 3 is given by@ FE = -2% n . - + . n - 2 n H . -+ %. n -EB D. -EB C.

'hich is a mat h e m a t i c al expr e s sio n for the 5a' of 2ass %ction, and is simply the ratio of the conc e n t r a tio n s of produc t s over react a n t s in E,uation 3. E,uation D can be re 'ritte n as@
-& +. + E = E - &!.
n

-EB #.

and so,
- &!. E = +E -& +.
n

-EB "<.

!e see the n that the extr a c tion coefficient E, 'hich is 'hat is det er mi n e d exp eri m e n t a lly -E,uatio n $. is proportion al to the e,uilibriu m cons t a n t s , to the nth po' er of the extr a c t a n t conce n t r a ti o n in the solven t phas e , and is invers ely proportion al to the nth po' er of the hydro g e n ion conc e n t r a ti o n in the a,u e o u s phas e . Thus FE can be readily calculat e d from exp eri m e n t a l dat a. 5et us no' consid e r furth er the relations hip s that exist bet' e e n the various par a m e t e r s involved in the solven t extr ac tio n of me t al s. Taking logarith m s of E,uation "< 'e obtain@ log E I log F E H n log -+ %. n log -+ . -EB "".

Thus by plotting log E vers u s p+ at cons t a n t -+ %. , 'e should obt ain a curve 'hos e slope is e,u al to n. ;urth er, if 'e 'rite this e,u a tio n as@ log E I log F E H n-log -+ %. H p+ . -EB "3.

the n plots of log E vers u s -log -+ %. H p+. 'ill give a straigh t line of slope n and an interc e p t e,u al to log FE. Such plots are useful in gettin g aroun d the proble m of having to reprod u c e extr ac t a n t conc e n t r a tio n s and identic al p+ value s in exp e ri m e n t a l studie s. 0y suita ble ma nip ula tion 'e see that 'e can obt ain an expr e s sio n involving G log -+., that is, p+. So " multiplying by @ n " " log E I log F E + log -+ %. log -+ . n n or log -+ . I p+ I " " log E log F E log -+ %. n n -EB "=. -EB ").

;or the situa tio n 'her e -for an %@4 ratio of ", that is, 'her e v I v . *< per cent of the met al is extr a c t e d into the orga nic phas e , the n 'e kno' that E I " from our definition of E in E,uation $. This is a uni,u e situ a tion since log E is no' &ero. Putting E I " in E,uation ") elimina t e s E, and@ <I " log F E + log -+ %. log -+ . n -EB "*.

0y re arra n gin g E,uation "*@ log -+ . I p+ I " log F E log - + %. n -EB "$.

The p+ given by E,uation "$ is that at 'hich *< perc e n t of the met al is extr a c t e d , and is kno'n variously as p+ *< , p+ <.* or p+ J . !e shall use the latter design a tio n here.

7o' the perc e n t met al extr a c t e d -P. 'ill vary 'ith variation in the %@4 ratio@ PI "<< E EH v v -EB "C.

'her e v and v are the volum e s of the a,u e o u s and orga nic phas e s , resp e c tiv ely. ;or the cas e 'her e vI v , the n vE v I ", but for all other cas e s the e,u a tio n for P has to be nor m alis e d , thus@
P= "<< E v E v E v E v +"

-EB "D. in ter m s

n

8e arra n gin g E,uation "C and e,u a tin g cons t a n t for E,uation "<, 'e hav e@

of the

e,uilibriu m

P -+ %. EI = FE n "<< P -+ . and taking logarith m s @

-EB "#.

log E log -"<< P. I log F E + n log -+ %. n log -+ .

-EB 3<.

E,uation 3< thus repr e s e n t s a family of sigmoid curves obt ain e d by plotting P vers u s p+, and the position of each curve on the p+ axis 'ill dep e n d only on FE and -+ %. . !e can, again derive an e,u a tio n for p+ J from E,uation 3<. :eviation s from the theor e tic al slope n in such plots 'ill indicat e that the extr a c tion is not as simple as describ e d , for exa m pl e , by E,uation 3, but may involve@ -i. me t al comple x a tio n in the a,u e o u s phas e such as acid hydrolysis and compl ex a tio n involving an anionic comp o n e n t of the a,u e o u s pha s e / add uc t forma tio n bet' e e n met al extr ac t a n t , diluen t or modifier/ compl ex e s and undiss ocia t e d

-ii. -iii.

form a tio n of inter m e d i a t e me t al comple x e s /

-iv.

polym e ris a tio n in the solven t phas e .

1n real situa tio n s in proce s sin g leach li,uors the syst e m s are cert ainly not as simple as sugg e s t e d by E,uation 3. Extraction coefficient s provide only an indication of the over all situa tion that can be ,uite compl ex in ter m s of individu al reaction s occurring in the syst e m . Acidic Extractants Extraction mec h a nis m s involving acidic extr a c t a n t s are mor e complicat e d to describ e, in a gen e r al 'ay, than for chelating extr ac t a n t s . !hile the sa m e ,ualitativ e consid er a tio n s apply, such as the influenc e of p+, extr a c t a n t and met al ion conce n t r a tio n, factors affecting the order of met al extr ac tio n and so on, the comp o sition of the extr ac t e d species is less predict a bl e. 0asically, the appro a c h take n to und er s t a n d i n g the extr ac tio n mec h a nis m s of such syst e m s is the sa m e as for chelating syst e m s . ;or exa m pl e , an e,u a tio n for the extr ac tio n of copp e r by the mono b a sic extr a c t a n t :3E+P% can be 'ritte n@ -EB 3".

'hich is of the sa m e form as E,uation 3. Systems Involving Ion Association Syst e m s involving ion associa tio n are much mor e difficult to analys e tha n thos e previously discus s e d . This difficulty arise s as a result of our lack of und er s t a n d i n g of species in conc e n t r a t e d solution s, that is, solutions of gre a t e r tha n abou t <." 2 ionic stre n g t h . Thus the usu ally acce p t e d e,uivale n c e of conce n t r a ti o n 'ith activity at lo' conce n t r a tio n s of salts canno t be applied, and the ,ua n tit a tiv e expr e s sio n s derive d for chelat e and acidic extr a c t a n t syst e m s beco m e ess e n ti ally ,ualita tiv e in ion associa tio n syst e m s . %ccordingly, much of the 'ork don e on such syst e m s is invaria bly empirical in natur e . Com m e r ci al proce s s e s involving ion associa tio n syst e m s employ long chain alipha tic prima r y -87+ 3 ., secon d a r y -8 l8 3 7+., tertiary -8 l8 3 8 ) 7. amin e s , or ,ua t e r n a r y am m o ni u m salts -8 l8 3 8 ) 8 = 7H X . as the extr ac t a n t . %ll thes e reag e n t s , 'hen dissolve d in a diluen t, aggr e g a t e to a gre a t e r or less er ext e n t. 0eca u s e of this aggr e g a tio n the nu mb e r of e,uilibria involved is a largely unkno' n factor and esp e ci ally so 'hen the e,uilibria involved in the a,u e o u s phas e are includ e d . Thus the nu mb e r of

e,uilibria re,uire d to describ e the ion associa tio n extr ac tio n of met als is ma n y time s that involved in, say, a chela t e extr ac tio n syst e m . %s note d abov e, a ma(or complication in amin e extr a c tion syst e m s is the molecular ass ocia tion of amin e salts into dimer s, trimer s , etc.@ 8 ) 7+ H .X -8 ) 7+ H .X . K -8 ) 7+ H .X . n -EB 33.

and one of the mor e import a n t factors affecting aggr e g a tio n is the nat ur e of the diluen t use d. The extr ac tio n of anionic met al chloro comple x e s by amin e s is us ed in com m e r ci al oper a tio n s such as the sep a r a tio n of cobalt from nickel. 1t is kno'n that nickel has little tend e n c y to form anionic chloro compl ex e s , 'her e a s cobalt has. ?se of this fact ena bl e s cobalt to be extr a c t e d from nickel in high chloride -L3 < < kgEm ) . solution by a tertiary amin e. This can be repr e s e n t e d by an e,u a tio n of the type@
H H 3 CoCl 3 = H 38 ) 7 + Cl M-8 ) 7 + . 3 CoC" = N H 3Cl

-EB 3).

Extraction of a met al 2nH , 'hich forms anionic comple x e s 'ith an anion % in the a,u e o u s pha s e can be repr e s e n t e d as an anion exch a n g e proce s s . ;or exa m pl e , if 'e take the cas e of the extr a c tion of uraniu m from sulph a t e solution by a tertiary amin e, the n the amin e mus t first be conv er t e d to an appro pria t e salt to provide the anion exch a n g e 'ith the met al species . This can be repr e s e n t e d by 2R3N + H2SO 4 (R3NH)2 SO 4 -EB 3=.

and is achiev e d by cont a c tin g the orga nic solution of the amin e -solven t phas e . 'ith an a,u e o u s acid, her e + 3 S4 = , to form the salt -8 ) 7+. 3 S4 = . Contac tin g this amin e salt solution -solve n t. 'ith an a,u e o u s solution of uran yl sulph a t e at the correct p+ results in the exch a n g e -extr ac tion. as illustra t e d in E,uation 3*@
3 ?4 3 -S4 = .3 3 H 3-8 ) 7 + . 3 S4 = -8 ) 7 + . = ?4 3 -S4 = . ) H S4 =

-EB3*.

Similarly, the extr a c tion of the neutr al uranyl sulph a t e , ?4 3 S4 = , can be repr e s e n t e d by@ -8 ) 7 + .3 S4 = H ?4 3 S4 = -8 ) 7 + .3 ?4 3 -S4 = .3 -EB3$.

The degr e e to 'hich extr a c tion of eith er an anionic or neutr al uraniu m sulph a t e specie s is involved dep e n d s on the uraniu m specie s pres e n t in the a,u e o u s phas e , 'hich in turn dep e n d s on the sulph a t e conc e n t r a ti o n and p+ of the a,u e o u s phas e . 1n acid sulph a t e syst e m s the import a n c e of p+ beco m e s mor e prono u n c e d than for nitrat e or chloride syst e m s as a

result of the dibasic natur e of + 3 S4 = , 'hich gives rise to the sulph a t e bisulph a t e e,uilibria. + 3 S4 = + H + + S4 = + S4 = + H + S4 3 = -EB3C. -EB3D.

Thus at high acid conc e n t r a ti o n s bisulph a t e is the ma(or anionic specie s , and as the acid conc e n t r a ti o n is decr e a s e d the sulph a t e ion beco m e s the pred o mi n a n t species . Systems Involving Solvation %noth e r import a n t group of extr a c tion syst e m s is that bas e d on the po' er of oxyg e n cont ainin g orga nic extr ac t a n t s to solvat e inorg a nic molecule s or compl ex e s . 0y such solvation the solubility of the inorg a nic specie s in the orga nic pha s e ma y be gre a tly incre a s e d . There are t'o main group s of extr ac t a n t s in this group/ thos e cont ainin g oxyg e n bond e d to carbo n such as eth e r -C 4 C., est er s - C448., alcohols -C 4+. and keton e s -CI4., and thos e cont ainin g oxyg e n bond e d to phos p h o r u s such as alkylpho s p h a t e est e r s - PI4.. 4ne distinguis hin g featur e bet' e e n thes e extr ac t a n t typ e s involves the role playe d by 'ater. The stron gly polar orga n o p h o s p h o r u s comp o u n d s comp e t e favour a bly 'ith 'ater and can replac e 'ater molec ul e s in the first hydr a tion sph er e of a me t al ion. !ith eth e r s and keton e s , 'ater is a nec e s s a r y part of the comple x, prob a bly forming bridg e s bet' e e n the orga nic and met al comp o n e n t s of the comple x throu g h hydro g e n bondin g. Thes e extr ac t a n t s can, by virtu e of solvation, extr ac t both acids and me t al comple x e s . 4ne mark e d feat ur e of extr a c t a n t s cont ainin g C 4 bond s is the high degr e e of me t al hydr a tio n that occurs in the solven t pha s e . ;or exa m pl e , in the extr ac tio n of ferric chloride into eth e r, salvation num b e r s as high as "3 hav e be e n report e d , 'hich mak e s the exist e n c e of solvat e s of specific comp o sition ,ue s tion a bl e. This, combin e d 'ith the fact that thes e syst e m s exhibit stron g non ideality in the orga nic phas e , eve n at lo' conc e n t r a tio n s , mak e s a gen e r al theor e tic al tre a t m e n t almos t impos sible. The mos t 'ell kno'n and mos t use d of the orga n o phos p h o r u s est er s is undo u b t e dl y tri n butyl phos p h a t e -T0P.. 0eca u s e of its 'ide use in the proce s sin g of nucle ar ma t e ri als, an almo s t be'ildering amo u n t of dat a is available on it and on similar rea g e n t s . 0ut des pit e this, gen e r al e,u a tio n s for me t al extr ac tio n s cann o t be given. Thes e syst e m s are comple x, 'ith fe' easily defina bl e species form e d , and 'ith direct similarities bet' e e n differe n t syst e m s .

%s a rule of thu m b , 'e can say that the extr ac tiv e po' er of phos p or u s cont ainin g extr ac t a n t s incre a s e s 'ith incre a s e in the num b e r of carbo n phos p h o r u s bond s over the series@ phos p h a t e O phos p h o n a t e O phos p hin e oxide. The solubility of neutr al orga n o p h o s p h o r o u s comp o u n d s in 'at er decr e a s e s in the order@ phos p hin e oxides L phos p hin a t e s L phos p h o n a t e s L phos p h a t e s . This is a result of the incre a sin g polar natur e of the phos p h o n yl group. 4n the other hand, the solubility is lo' but as the acid conce n t r a tio n is incre a s e d solubility incre a s e s , in som e cas e s to prohibitive value s. Extractiv e of met als by T0P from various acidic me dia app e a r s to involve ", 3 or ) molecule s of T0P in the extr a c t e d specie s . Som e propo s e d extr a c t e d specie s are given in Table " . Ta l e $ 6 Some Extract a bl e 2etal G T0P Species . Syst e m ?4 3 -74 ) . 3 G T0P ?Cl = G T0P 2o-61. G +Cl G T0P Ta; * G T0P 6-6. G +Cl G T0P 7b; * G T0P Extract e d Specie s ?4 3 -74 ) . 3 3T0P ?Cl = 3T0P 2o4 3 Cl3 3T0P Ta; * +; 3T0P +64 * Cl3 T0P 7b; * +; )T0P

Some Practical Considerations %pplication of som e of the theor y discus s e d abov e asp e c t s of solven t extr ac tio n are provide d belo'. Extraction Coefficient (E) This coefficient is a me a s u r e of ho' 'ell a solven t 'ill extr ac t a me t al or met als und er given exp e ri m e n t a l condition s. 1t is a num b e r -has no units., is conc e n t r a tio n dep e n d e n t , and is not a cons t a n t . The value of E dep e n d s on factors such as te m p e r a t u r e , p+, pha s e ratio, extr ac t a n t conc e n t r a ti o n, met al conc e n t r a tio n, and me t al compl ex a tio n in both phas e s . ;or exa m pl e , the variation of E as a function of the phas e -%@4. ratio is sho' n in ;igure 3 . 4nly the phas e ratio 'as varied in this study. 0y itself, a value of E has really no me a nin g, simply bec a u s e it is dep e n d e n t on the abov e variabl e s . Thus to say that an extr a c tion syst e m is good simply bec a u s e E is high, 'ithou t giving the condition, is again an exercis e in futility. to the practical

(i5ur e 2 6 Effect of %@4 8atio on 2etal Extraction Extractant Concentration ;or a given me t al ion conc e n t r a ti o n in the a,u e o u s phas e , E 'ill incre a s e 'ith incre a s e in extr a c t a n t conc e n t r a ti o n, other factors being cons t a n t / the conver s e is also true. This effect is ded uc e d from E,uation "<, and is illustra t e d in ;igure )

(i5ur e 3 6 6ariation of Extraction Coefficient for ?raniu m as a ;unction of PT0PQ The distribu tion curve for the extr a c tion of a me t al, as a function of p+, 'ill shift to'ar d s lo'er p+ value s as the extr a c t a n t conce n t r a tio n incre a s e s . This is predict e d by E,uation "$, and illustra t e d in ;igure * . 5et us ass u m e that the syst e m has a p+ J of ).* and the E G p+ plot is as indicat e d by the solid line, giving a value of E I " und er the s e conditions . 1ncre a sin g the extr ac t a n t conce n t r a tio n 'ill result in the extr a c tion of mor e me t al, and since the amo u n t of me t al in the syst e m is fixed, then E mus t incre a s e at this p+. This gives us, say, a point at E I *. 7o' for

the seco n d syst e m -high extr a c t a n t ., this point mus t fall on a ne' curve that 'e 'ould obt ain und e r the exp eri m e n t a l conditions given, and 'hich is repr e s e n t e d by the dott e d line. Convers ely, a decr e a s e in extr a c t a n t conc e n t r a ti o n 'ill shift the curve to'ard s higher p+ value s.

(i5ur e * 6 Effect of Extract a n t Conce n t r a tio n on 2etal Extraction Effect of p %s predict e d by E,uation 3, all extr ac t a n t s of the acidic or chela tin g type s libera t e hydrog e n ion on the extr ac tio n of a met al. The gre a t e r the amo u n t of me t al extr a c t e d , then the mor e hydro g e n ion is produc e d . 1ncre a sin g hydro g e n ion conce n t r a ti o n in the a,u e o u s phas e 'ill, of cours e, shift the e,uilibriu m in E,uation 3 to the left, 'hich 'ill result in a decr e a s e in met al extr ac tio n. E,uation ) sho's that the higher the e,uilibriu m p+ of a syst e m , the lo'er 'ill be the conce n t r a ti o n of extr ac t a n t nee d e d to achiev e a given met al extr a c tion, and vice vers a. ;or exa m pl e , at a phas e ratio of ", incre a sin g the p+ by one unit 'ill incre a s e E by an order of ma g nit u d e for n I ". ;or n I 3 an incre a s e in E of "< order s of ma g nit u d e is predict e d , and so on. This is sho'n in ;igure * for n value s of " to =.

(i5ur e ) 6 Effect of 2etal 4xidation Stat e -n. on the 8ate of Chang e of Extraction Coefficient 'ith p+. A!ueous Phase Composition The typ e and conc e n t r a ti o n of met al compl ex e s in the a,u e o u s phas e can dra m a tic ally affect the extr a c tion of a met al. >ener ally 'e can exp e c t that 'her e a me t al comple x in the a,u e o u s phas e has a stability gre a t e r than that of the met al extr ac t a n t comple x, it 'ill not be extr a c t e d . sho' s the affect of incre a sin g me t al comple x a tio n in the a,u e o u s phas e on the extr a c tion of Co and 7i by :3E+P% from an am m o ni a c al syst e m . Presu m a b l y the form a tion of ion associatio n compl ex e s , such as Co-7+ ) . * 4+ 3 S4 = H , inhibits the form a tion of an extr a c t a bl e cobalt species . This particular affect is reversible. "etal Ion Concentration The conc e n t r a ti o n of free extr a c t a n t at e,uilibriu m -+%. ;, is given by@ -+ %.; = -8%.T -2. n%. -EB3#.

'her e -+%. T is the initial total conce n t r a tio n of extr ac t a n t , and -2.n%. is the conce n t r a tio n of me t al extr a c t a n t species . 1f the me t al conc e n t r a ti o n in the syst e m is incre a s e d , oth er condition s rem ai ning cons t a n t , -2.n%. 'ill incre a s e 'ith the result that -+%. ; 'ill decr e a s e , 'ith a relativ e decr e a s e in E. %n exa m pl e of this effect is sho' n in Table 3 . Ta l e 2 6 Effect of 2etal 1on Conce n tr a tio n on the Extraction Coefficient of ?raniu m P?4 3 -74 ) . 3 Q 2 <.<= <.3" ".$D E *.C 3.$ <.=

%gain, 'e see that E is dep e n d e n t on the exp eri m e n t a l conditions. Solvent #oading Capacity 4f ma(or import a n c e in com m e r ci al solve n t extr a c tion proc e s sin g is the limiting portion of E or log E p+ plots. The exte n t of the limiting portion of such curve s dep e n d s on factors such as the p+ at 'hich hydrolysis or comple x a tio n of the met al ion occurs in the solven t phas e , or loading cap acity of the solven t. 2any solven t extr a c tion proce s s e s are oper a t e d in this region simply bec a u s e this is 'her e maxi m u m utilisation of the solven t occurs und er the particular set of conditions used. !hile it is not abs olut ely nec e s s a r y, nor inde e d possible -for exa m pl e , as a result of high viscosity of the solven t. to oper a t e at the point of maxi m u m solve n t loading, doing so

ens ur e s that a minimu m solve n t consid er a bl e econo mic import a n c e .

flo' rate

is re,uire d,

'hich is of

The maxi m u m loading obtain a bl e by a solve n t dep e n d s , amo n g oth er things, on the total available or free extr ac t a n t and on the solubility of the me t al extr a c t a n t species , rath e r than any limit in the ext e n t of extr a c tion. The solubility of an extr a c t a bl e species dep e n d s in larg e part on the diluent used in the solven t, and also on the modifier if pres e n t . Poor solubility of an extr ac t e d specie s forma tio n of a third phas e , inter m e di a t e and the a,u e o u s phas e . To inhibit third usu ally add e d to the solven t to incre a s e specie s . results in ma n y cas e s in the in den sity bet' e e n the diluent pha s e forma tio n a modifier is the solubility of the extr ac t e d

%n approxi m a t e idea of the loading cap acity of a particular solven t can be calculat e d kno'ing the comp o sition or struct u r e of the extr a c t e d species , and the conc e n t r a ti o n of the extr ac t a n t in the solven t. ;or exa m pl e , Felex "<<, a subs tit u t e d D hydrox y, ui nolin e, forms a "@3 met al@ e x tr a c t a n t comple x 'ith cupric ion -Cu 3H .. Thus a <.*2 solution of Felex "<< in an inert diluen t should hav e a maxi m u m loading cap a city of <.3*2 copp er, that is, <.3* x $).* I "*.# kg Cu m ) . This agr e e s 'ell 'ith the exp e ri m e n t a lly det er mi n e d loading of such a solve n t, na m el y "*.< kg Cu m ) . Similarly, Felex "<< forms a )@" compl ex 'ith ferric ion -;e )H ., thus the sa m e solve n t should load <.* x **.D I #.) kg ;e m ) . $inetics of Extraction !e hav e note d earlier that solven t extr ac tio n is an e,uilibriu m proce s s , and our discus sion s hav e reflect e d this. +o'ev e r, the rate at 'hich e,uilibriu m is reac h e d is also an import a n t factor, and in solven t extr a c tion proc e s sin g the kinetics of the syst e m gover n s , amo n g oth er things, the throu g h p u t of the proc e s s . Thus 'ith slo' kinetics the rete n tio n time in the extr ac tio n stag e s mus t be gre a t e r than for a syst e m involving fast kinetics. 6ery fast kinetics of extr ac tio n, for exa m pl e, allo's the use of cont a c t o r s 'hich hav e ret e n tio n time s in the order of secon d s -such as centrifug e s . and 'hich allo' for high flo' rat e s . >ener ally, me t al extr ac tio n is gover n e d by ma s s tran sf e r and diffusion rate s 'hich are, on the 'hole, fairly rapid. 2ost che mic al reaction s involving ionic typ e reaction s are rapid, 'her e a s the rat e s of reaction s involving chela t e forma tio n can vary over a consid er a bl e rang e . 4ther factors affecting extr ac tio n rate s are viscosity of the amo u n t of agita tio n, and the te m p e r a t u r e of the syst e m . phas e s ,

1n a het er o g e n e o u s syst e m such as 'e hav e in solven t extr ac tio n the rate of extr ac tio n of a met al 'ill dep e n d , in large me a s u r e , on the surfac e are a of the disper s e d phas e . !e should note that in a cont a c t o r one phas e 'ill be disper s e d -the disper s e d phas e . in the other -the

continu o u s pha s e ., and this dep e n d s ess e n ti ally on the conditions initially pres e n t at the start of agit a tion of the pha s e s . The surfac e are a of the disper s e d phas e 'ill dep e n d on the amo u n t of agita tion, that is, on the ener g y input to the syst e m . +o'ev e r, it should not be thoug h t that the gre a t e r the agit a tion the gre a t e r the rat e of met al extr ac tio n. Too muc h en er g y input can result in the forma tio n of stable or se mi sta bl e emulsions . ;urth er m o r e , decr e a s i n g the bubble si&e of the disp er s e d phas e can res ult in making the bubble s res e m b l e rigid sph e r e s . 1n this condition ther e is no intern al mov e m e n t 'ithin the sph e r e s , no ne' surfac e s are produc e d , and the extr a c t a n t 'ithin the sph e r e cann o t get to the surfac e to reac t 'ith me t al ions. Cons e , u e n tl y, the extr ac tio n rat e is slo'. %s 'ith all reaction s the slo'es t step in the proc e s s is rate det e r mi nin g, that is, it controls the over all rate of the syst e m . ;or exa m pl e , the forma tio n of an extr a c t a bl e compl ex ma y be much slo'er than the rat e at 'hich the comple x is extr ac t e d into the orga nic pha s e @ 2 n H + n+ % 2% n + n+ H 2% n 2% n thus the rate det er mi nin g step is E,uation )<. The rate of me t al extr a c tion may also be a function of the inertn e s s of the hydr a t e d me t al ion to subs tit u tion, that is, to the replac e m e n t of 'at er of hydr a tio n by a comple xing reag e n t . 1f 'e consid er me t al comple x a tio n rat e s in thes e ter m s , the rat e at 'hich the 'at er s of hydr a tio n are replac e d by oth er 'ater molecule s should give som e indication as to the rat e at 'hich compl ex a tio n 'ith reag e n t s oth er tha n 'at er 'ill occur. The rat e const a n t s for 'at er exch a n g e for som e met als follo' the order@ Cu 3H L 2n 3H L ;e 3H L Co 3H L 7i3H L ;e )H L Cr )H Thus it is not surprising that ferric compl ex e s are, on the 'hole, slo'ly extr a c t e d , 'her e a s Cu 3H and 2n 3H are usu ally extr ac t e d rapidly. This kinetic effect is cert ainly a ma(or reas o n 'hy specificity for copp e r over iron can be achiev e d using chelating extr ac t a n t s such as Felex "<< or the 51X rea g e n t s . 4ther reas o n s for slo' extr a c tion kinetics are steric re arra n g e m e n t s bet' e e n specie s in the form a tio n of an extr a c t a bl e compl ex, or stron gly hydrolys e d or other'is e comple x e d me t al in the a,u e o u s phas e that results in slo' rever sibility of such comple x e s to ones am e n a b l e for comple x a tio n 'ith the extr a c t a n t .
fast slo'

-EB )<. -EB )".

% timely exa m pl e of steric inhibition is sho' n by the syn isom e r s of 51X extr a c t a n t s . Thes e are subs tit u t e d o hydrox y ben&o p h e n o n e oxime s , and can exist in t'o isom e ric forms, syn and anti@
R

anti isom e r

N O H

O H

H O

O H

syn isom e r 4nly the anti isom e r forms me t al comple x e s at any appr e ci a bl e rate, the syn isom e r doing so only slo'ly. This is a result of the special orient a tio n of the electro n pair on the nitrog e n ato m in the anti isom e r being adv a n t a g e o u s l y situ a t e d for comple x a tio n 'ith a met al ato m@
R

H O

N M

'her e a s in the syn isom e r it is orient e d in a direction unsuit a bl e for me t al comple x a tio n. %noth e r factor affecting extr a c tion rate s is that of tran sf e r rat e of a comple x acros s the a,u e o u s orga nic pha s e boun d a r y. 8ece n t studie s hav e indicat e d that, at leas t for the cas e of chelating extr ac t a n t s , the forma tio n of the extr a c t a bl e me t al chela t e occurs at the a,u e o u s orga nic interfac e . %ccordingly, interfacial ener gi e s can hav e a significant effect on rate s , and 'hich are the m s el v e s det e r mi n e d by the syst e m comp o n e n t s . Thus resolution of the basic reas o n s for extr ac tio n rat e chan g e s in any one syst e m is a compl ex und e r t a kin g. 8ate dat a available on SX syst e m s , and eve n on oth er syst e m s such as are use d in an alytical che mis tr y, are not very gre a t . 0ecau s e of this, and bec a u s e of the ma n y factors 'hich influenc e the kinetics, it is difficult to mak e any gen e r alis a tion s reg ar din g this sub(ect. 0ut 'hat e v e r the reas o n s , the kinetics of met al extr ac tio n are import a n t in solven t extr a c tion proce s s e s .

010514>8%P+A ". 3. ). =. *. 2arcus, A., and Fertes, %. S., R1on Excha n g e and Solven t Extraction of 2etal Complex e s R, !iley 1nters cie n c e , 7e' Aork, 7.A., "#$#. Proce e din g s of Confer e n c e s . the 6arious 1ntern a tio n al Solven t Extraction

+ans e n , C., R8ece n t %dvanc e s in Solven t ExtractionR, Perg a m o n , 5ondon, "#C". Stary, S., RThe Solven t Extraction of 2etal Chelat e s R, Perg a m o n , 4xford, "#$=. :e, %. F., Fhopkar, S. 2., and Chalm e r s , 8. %., RSolvent Extraction of 2etalsR, 6an 7ostra n d 8einhold, 5ondon, "#C<.

SECTION II

EXTRACTANTS, DI !ENTS, AND "ODI#IERS

Extractant Classi$ications There are ess e n ti ally thre e main classification s for extr ac t a n t s @ acidic, basic, and neutr al. The acidic and basic are also referr e d to as cationic and anionic, res p e c tiv ely. Some extr ac t a n t s are sho'n in This order is illustra t e d in ;igure $ for sev er al met als from a sulph a t e solution. 6ariation s can occur, 'hich are usu ally influenc e d by the natur e of the a,u e o u s pha s e on the forma tio n of met al compl ex e s that effect their extr a c tion. Thus the order of extr a c t a bility of som e divalen t met als from "7 +Cl solutions using *< volum e per cent :3E+P% is@ . Acidic Extractants %cidic extr ac t a n t s 'hich are of use, bec a u s e of cost andEor insolubility in 'at er, are alkylpho s p h o ric, sulpho nic, alipha tic monoc a r b o x ylic acids and naph t h al e n e deriva tiv e s . Al%ylphosphorus Acids This group includes esters of orthophosphoric, phosphonic and phosphinic acids, and similar compounds containing polyfunctional groups. 4f these, alkylphosphoric acids have proved to be the most versatile, especially di-3 ethylhexyl. phosphoric acid -:3E+P%.. ?se of this reagent probably dates from "#=#, and it has been used commercially for the extraction of many metals including uranium, cobalt and nickel, rare earths, and vanadium. Some particular advantages of the use of :3E+P% in solvent extraction processing are its chemical stability, generally good kinetics of extraction, good loading and stripping characteristics, lo' solubility in the a,ueous phase, versatility in the extraction of many metals, and its availability in commercial ,uantities. 1t is probably fair to say that :3E+P% is still the most versatile of all the extractants commercially available today. %s a result of its popularity, a considerable amount of information is available on this and many similar reagents. 1n the past several years there has also been increased interest in the potential applications of phosphonic and phosphinic acids. These organophosphorus acids derivatives can be represented structurally as follo's@

'ith the active group the LP-4.4+ 'hich is responsible for their extractive properties. !hen one % is an alkyl or aryl group the resultant compound is an organophosphonic acid derivative 'hereas 'hen both %Ts are alkyl or aryl the product is an organophosphinic acid derivative.

% fact 'hich influences extraction is the ability of these acids, like carboxylic acids, to form diners in solution -"".. 1ndeed :3E+P% in many diluents is dimeri&ed -"3 "*. having the structure@

'hich could be extracted at a lo'er p+ than normally occurs 'ith :3E+P%. This extractant 'as developed and supplied by Shell Chemicals as S2E ="D and by :aihachi Chemical, Sapan as PC DD% -)<.. The reagent is kno'n as 3 ethylhexyl phosphonic acid mono 3 ethylhexyl ester, sho'n belo' .

Cyanex 3C3 is a further development in the alkyl phosphorus reagents. This is a phosphinic acid extractant, :i-3,=,= tri methylpentyl. phosphinic acid, 'ith the structural formula belo' -)"., and manufactured by Cytec Canada.

:i -3 ethylh e x yl.p h o s p h o ric acid -:3E+P%. is perh a p s the mos t popular, particularly for use in acid solution s-" "3.. The effect of anions on the extr a c tion of met als using :3E+P% is exp e c t e d to incre a s e in the order@
C"4 O C4 3 O S4 3 = O 7 4 ) O Cl ) =

This is also similar for carbox ylic acids. The order of extr ac t a bility of met al ions by acidic extr ac t a n t s gen e r ally parallels the order of the hydrolysis cons t a n t s of met al ions, som e of 'hich are sho'n in Table ) . Ta l e 3 6 +ydrolysis Const a n t s of Some 2etal 1ons -")..

1on 0i)H ;e )H Cr )H %" )H Cu 3H Pb 3H Un 3H

Pka ".$ 3.3 ).D *." $.D C.D D.D

1on Co 3H Cd 3H ;e 3H 7i3H 2n 3H 2g 3H Ca 3H

PFa D.# #.< #.* "<.$ "<.$ "".= "3.$

This table explains the rath e r 'ell kno'n stat e m e n t that me t als extr ac t bes t at a p+ (ust belo' that at 'hich they hydrolys e . This order is illustra t e d in ;igure $ for sever al me t als from a sulph a t e solution. 6ariation s can occur, 'hich are usu ally influenc e d by the nat ur e of the a,u e o u s pha s e on the form a tion of me t al compl ex e s that effect their extr ac tio n. Thus the order of extr a c t a bility of som e divale n t me t al s from "7 +Cl solutions using *< volum e per cent :3E+P% is@ Un L >a L Pb L 2n L Cu L Cd L 7i L 2g L 0a, Sr, Co. The effect of ion ass ocia tion on the extr ac tio n of cobalt and nickel from an alkaline am m o ni u m sulph a t e solution is sho' n in .

(i5ur e - 6 Extraction of 2etals by :3E+P% from Sulph a t e Solution.

;igure C @ Effect of Sulph a t e on the Extraction of Co and 7i by :3E+P% at p+ "".

Table = @ So 7 e Co7 7 o n E8tra 9 t a n t s !or us e in H:;ro 7 e t a l l u r 5 : #

#D

Car&oxylic Acids The use of alipha tic carbox ylic acids has bee n report e d mainly for acidic solutions -"= "#., but the use in alkaline solutions app e a r s attr a c tiv e -3<.. Thes e extr ac t a n t s oper a t e by a cation exch a n g e mec h a nis m @
2 H X + 8C44+ 8C442 + + H + X

-EB )3.

%n order of extr ac t a bility for C C G C # alipha tic carbox ylic acids -)C,)D. has bee n report e d as@
Sb =H L 0i )H L ;e )H L Pb 3H L %l)H L Cu 3H L Cd 3H L Un 3H L 7i3H L Co 3H L 2n 3H L Ca 3H L 2g 3H L7a H

% typical order of me t al extr ac tio n using bro mo lauric acid-3 ). is sho' n in ;igure D , and for 6ers atic # -3=. in ;igure # . The effect of -compl ex form a tion in the a,u e o u s pha s e . is sho'n in Error@ 8efere n c e sourc e not found for the extr ac tio n of cobalt from an alkaline am m o ni u m sulph a t e solution -3*..

(i5ur e 8 6 Extraction of 2etals ?sing bro mo auric acid.

(i5ur e 9 6 Extraction of 2etals ?sing 6ersatic #.

(i5ur e $0 6 Effect of Salt Conce n t r a tio n on the Extraction of Cobalt ?sing <.*2 6ersatic #"".

'asic Extractants ;or all practical purpos e s thes e extr a c t a n t s exch a n g e . extr ac t a n t s . Solven t extr a c tion are the amin e -anion proc e s s e s hav e be e n

dev elo p e d 'hich use eith er primar y - 7+ 3 . -3$ )3./ seco n d a r y - 7+. -3D,3#,) )./ tertiary - 7. -)= =). or ,uart e r n a r y amin e s -=<,==,= *.. 1n gen e r al, extr a c tion of compl ex met al anionic specie s from chloride me dia 'ith amin e s follo's the order@ ,uart e r n a r y L tertiary L secon d a r y L primar y 'hich is similar to the sulph a t e syst e m . Extraction of cobalt from +Cl solution tertiary amin e s is sho' n in ;igure "" . using prima r y, seco n d a r y, or

The effect of the halide salt conc e n t r a tio n, in contr a s t to the acid is sho'n in ;igure "3 for the extr a c tion of ferric iron. %lthoug h tertiary amin e s are selectiv e for the extr a c tion of uraniu m from sulph a t e solutions in the pres e n c e of iron and thoriu m, the primar y and secon d a r y amin e s are not selectiv e. The differe n c e in extr a c tion of prima r y and secon d a r y amin e s in such a syst e m are sho'n in ;igure ") . The extr ac tio n of bas e me t al s using tertiary amin e s is sho' n in ;igure "= , as 'ell as in ;igure "* . The chloride ion effect is sho' n in ;igure "$ . The effect of + 3 S4 = conc e n t r a tio n on the extr a c tion of me t als using a tertiary amin e is sho' n in ;igure "C .

(i5ur e $$ 6 Effect of +Cl conce n t r a tio n on the Extraction of Cobalt by :ifferen t %mines.

(i5ur e $2 6 Effect of Salt and %cid Conce n t r a tio n on the Extraction of 1ron -111. by %mines.

(i5ur e $3 6 Comp a ris o n of %mines for ? and Th Co extr ac tio n. Effect of Stag e 'is e Extraction on the Extract Purity.

(i5ur e $* 6 Extraction of 2etals ?sing Tertiary %mine from +Cl 2edia.

(i5ur e $) 6 Extraction of 2etals ?sing <." 2 T"<% from +Cl 2edia.

(i5ur e $- 6 2etal Extraction as a ;unction of Chloride Conce n t r a tio n 'ith a Tertiary %mine.

(i5ur e $. 6 2etal Extraction as a ;unction of + 3 S4 = Conce n t r a tio n ?sing a Tertiary %mine.

(eutral Extractants The neutr al extr a c t a n t s are bes t exe m plified by tri n butyl phos p h a t e -T0P.,'hich has had the mos t use in the nucle ar field in chloride or nitrat e syst e m s -=$ *3.. %lthoug h other neutr al orga n o p h o s p h o r o u s extr a c t a n t s hav e gre a t e r extr a c tion po' er, such as trioctyl phos p hin e oxide -T4P4., the T0P is consid e r a bly less exp e n siv e. >en er ally the extr a c tiv e po' er of phos p h o r o u s cont aining extr a c t a n t s incre a s e s 'ith incre a s e in the carbo n phos p h o r o u s bonds over the series phos p h a t e phos p h o n a t e phos p hin e oxide. T0P can be use d at "<< per cent conc e n t r a ti o n, as 'ell as at lo'er conc e n t r a ti o n s in a diluen t. 1n the refining of uraniu m and &irconiu m, for exa m pl e , 3* to *< per cent T0P is use d -=C.. T0P has also bee n found to be useful in the extr a c tion of bas e me t als from chloride solutions . The extr a c tion of som e bas e me t al s by T0P from chloride solutions is sho' n in ;igure "D . The mec h a ni s m of extr ac tio n is gen e r ally consid er e d to involve coordin a tio n of the phos p h o r yl -PI4. group directly to me t al s, as in ?4 3 -74 ) . = 3T0P. Chelating Extractants (Acidic Extractants) 4rga nic chela tin g extr ac t a n t s are thos e that cont ain donor group s cap a bl e of forming chelat e s 'ith me t al ions. % reag e n t used ext e n siv ely in an alytic al che mis tr y is D hydrox yl, uinoline. The chela t e form e d by this rea g e n t 'ith copp e r is sho'n as@

(i5ur e $8 6 Extraction of 0ase 2etals 'ith T0P.

Com m e r ci al chela tin g extr a c t a n t s of this typ e hav e be e n dev elop e d by both >ener al 2ills -51X$), $=, $*7, and C<. and %shlan d Che mic als -Felex "<<.. They hav e be e n used succe s sf ully in the extr a c tion of copp e r from acidic solutions -*) **., as 'ell as from alkaline solutions -*$,*C.. The gen e r al reaction can be 'ritte n@

Chelatin g extr ac t a n t s prob a bly offer the bes t appro a c h to the selective extr a c tion of met als , but are mor e difficult to strip than say acidic extr a c t a n t s , re,uiring from "*< to )<< g + 3 S4 = Elitre. Solvents Containing "ixed Extractants The ma(or ob(ectiv e in using mixed extr ac t a n t s is to take adv a n t a g e of the syn er gis tic effects 'hich can result. Since the early 'ork on the syn er gis tic effects of mixe d extr a c t a n t s -*D $"., ma n y syst e m s hav e bee n inves tig a t e d . 2ost of the 'ork has be e n conc er n e d 'ith mixtur e s of chela tin g ag e n t s plus neutr al extr ac t a n t s , and alkylphos p h a t e s plus neutr al extr ac t a n t s . 2ixture s of 51X$) and carboxylic acids hav e be e n inves tig a t e d for syn er gis tic effects in the extr a c tion of copp e r, nickel, cobalt and iron -$3.. 1n ;igure "# is sho' n the syner gis tic effect of the mixtur e of 51X$) and :3E+P% on the extr a c tion and sep a r a tio n of copp er from cobalt and nickel -$)..

(i5ur e $9 6 ?se of 2ixed Extract a n t for the Extraction of Cu, 7i, and Co. )iluents >ener ally the diluent, 'hich usu ally mak e s up the ma(or portion of the solven t pha s e , should be inert 'ith resp e c t to the extr ac t a n t , modifier and a,u e o u s phas e , and be insoluble in the a,u e o u s phas e . %lso, the extr a c t a n t and modifier mus t be soluble in the diluent. There are ma n y inert orga nic li,uids available com m e r ci ally for use as diluent s for solve n t extr a c tion proce s s e s . Thes e ma y rang e from ess e n ti ally alipha tic to ess e n ti ally aro m a tic. Some of the com m o n ones are sho'n in Table *a and *0. ;or reas o n s of safet y, it is nec e s s a r y to choos e a diluen t that has a flash point abov e "3< ;. Thus mos t of the diluent s listed hav e flash points 'ell abov e that te m p e r a t u r e . Table sho' s the effect of mixing the extr a c t a n t and the diluen t on the flash point.

Ta l e )a6 Some Com m e r ci ally %vailable :iluent s .

;lash :iluent 1sopar 5-%. 1sopar E -%. 1sopar 2-%. 7orpar "3 -%. Esso 5ops -%.V :X)$=" -%. Shell "=< -0. 7apole m =C< -C. Escaid ""< -%. Shell 5ivestock Spray -0. 2entor 3# -%. Shell Parab a s e -0. Escaid "<< -%. 7S "== -%. 7S "=D: -%. Solves s o "<< -%. Solves s o "*< -%. Xylene -%. +%7 -%. Cyclohex a n e -E. Chevro n =<5 -:. Chevro n )C< -:. Chevro n ==5 -:. Chevro n ) -:. Chevro n =3* -:. Chevro n 54S -:. Chevro n 3* -:. Point ; "== "=* "C3 "*$ "*3 ")* "=" "C* "$D 3C< 3D< 3"< "$D "=< "$< ""3 "*" D< "<* "=" "3C "*= "=* "=3 ")< ""* Compo n e n t %nalysis %rom a ti c <.) <.<* <.) <.$ 3.C $.< $.< "".C 3.= "* "* Paraffin #3.C ##.#= C#.# #C.# *".D =* =* =D.$ )#.# =D =D 7apht h e n es C.< "#.C "." =*.= =# =# )#.C *C.C )C )C 3< C <.C$C <.C3) <.CD3 <.C*" <.C#$ <.C#) <.CD* <.D"" <.D<D <.D"# <.D<< <.CDD <.C#< 0oiling Point ; )C) 3=< =<* )D= )D) )$" )$= ="< )D< *"3 *<< =3D )C$ )<.# #3 #< #D "<* C$ 3C C) DD 3$ )) #= Fauri 0utan ol 3C 3D 3C Solubility Para m e t e r C.3 C." C.)

6iscosity %t 3* C ".$< )."= ".$D 3.) "."$ * 3."< 3.*"

)).$ )3 ))

C.C

3< "$ =.* #D.# #C.< ##.C DD.* CD < $# #D 3 < ##

*$.$ =3 )D.$ "." ).< <.) =."

3).= =3 =)

".CD ".$< )
D.D D.C C.# C.D C.3

<.DC$ <.D#* <.DC< <.#)) <.DD$ <.C*D <.D#) <.DDD <.CDC <.CC# <.DC*

)"* )C< 3D" ))C )$< )=$ )$$ )$< )$< )*< )"$

"."# D <.$3 ".#C *

*.D "<<

-%. Esso or Exxon -0. Shell -C. Ferr 2c>ee 4thers V7o' Escaid 3<<

-:. Chevro n

-E.

Table *b@ S< e ll C<e 7 i 9 a l s %ilu e n t s

SHELLSOL A%AI &TY DENS '(C )*+", -OI IN. RAN.E /C # ASH POINT /C COND&TY 0S+m S1P1 RE ATI%E E%AP1 RATE %ISC1 2 34/C cSt ANI 1 PT1 /C S!R# TENS mN+m CO"P1 5 "+" P N A

^2046 2046AR ^232" &ARA'ASE (70 (80 (90 (100 (120 A100 A1"0 A200

Austra S. A !r. A#r$%a N.A !r Aust ) A#r ) Eur N * S A !r$%a Eur+,! Eur+,! ) Aust Eur+,! A-- L+%at$+.s A-- L+%at$+.s Aust

811 810 811 787 790 800 810 80" 82" 87" 883 992

198-234 210-260 21"-2"0 217-329 200-247 200-248 22"-27" 23"-278 247-326 1"6-172 181-210 233-271

78 84 87 86 79 80 9" 106 12" 43 64 101

<10 0 <10 <10 <10 <10 <10 <10 <10 4"0 4"0 4"0

8 8 8 7 8 8 8 8 8 9 9 9

0.01 0.01 0.01 0.01 0.01 0.01 <0.01 <0.01 <0.01 0.2 0.07 0.01

1.8 1.8 1.9 3.6 2.0 2.6 2.7 3.2 ".9 0.9 1.2 2."

62 62 69 90 7" 7" 82 82 8" 14(M) 14(M) 14(M)

30 30 30 28 26 26 26 28 40 29 30 3"

63 61 60 42 6" 32 60 60 64 0 0 0

18 21 22 "8 3" 68 40 40 3" 0 0 0

19 18 18 <0.1 0.3 0." <0.1 0." <1.0 99 100 100

S< e ll s o l 20 * - AR E=a> o r a t i o n Rat e Eva0oration Rate

0/8 l+m3+da6 0/6 0/4 0/2 0 1 2 3 4 " 6 7 8 9 10 11 12 13 14 1" 16 17 18 19 Time, da6 S0!--s+- 2046 AR ($-u!.t 1 ($-u!.t 2

Ta l e -6 Effect of Extract a n t and :iluent on the ;lash Point of the Solven t 2ixture. ;lash Point ; TCCV T4CVV ")# "=$ "*) "$#

Sam pl e Shell "=< ;lash 7apht h a *< vol W T0P in Shell "=< ;7 -fres h mixtur e , non e,uil. *< vol W T0P in Shell "=< ;7 -use d, stripp e d solven t. *< vol W T0P in Shell "=< ;7 -use d, e,uil 'ith +74 ) .

"$D," $ =

"C$," C D

V T%> clos e d cup test. VV T%> ope n cup test.

The choice of a diluent cann o t rea dily be predict e d , and should only be select e d after exp eri m e n t a l 'ork 'ith sev er al possible ones in cont a c t 'ith the actu al feed solution. %lthoug h gen e r ally it is ass u m e d that the diluent is in fact inert and does not ent e r into the mec h a ni s m of extr a c tion, cert ain diluen t s can assis t and enh a n c e the extr a c tion. The effect of alipha tic cont e n t of the diluen t on the sep a r a tio n of rare eart h s is sho'n in ;igure 3< and -$=.. The influenc e of the comp o sition of aro m a tics , par affins, or naph t h e n e s is sho'n to be mor e in som e syst e m s tha n in oth er s 'ith res p e c t to extr a c t a bility and sep ar a tio n of met als, as de m o n s t r a t e d in ;igure 3", and 33 for the sep a r a tio n of Co 7i by :E+P%. 1n ;igure 3) and 3= are sho'n the effects of diluen t comp o sition on the extr ac tio n of Cu by eith er an oxime or a subs tit u t e d hydroxy, uin oline. ;igure 3* sho' s a su m m a r y of the effect aro m a ticity on extr a c t a bility as det er mi n e d by the typ e of extr a c tion syst e m .

#i*7re 348 E##!%t +# Natur! +# ($-u!.t +. t0! E1tra%t$+. +# Rar! Eart0s.

(i5ur e 2$6 Effect of %roma tic Conte n t on Sep ar a tio n of Cobalt from 7ickel 'ith :E+P%.

(i5ur e 226 1nfluenc e of Compo n e n t s of :iluent on the CoE7i Sep ar a tio n.

(i5ur e 236 Effect of 7apth e n e s and Paraffins on Extraction of Copp er 51X $7.

(i5ur e 2$ Effect of %roma ticity on Extraction of Copp er and Phas e Sep ar a tio n 8ate -sec. ?sing Felex "<<.

(i5ur e 2)6 Effect of 2echa nis m of Extraction and %roma ticity on Extract a bility.

The polar nat ur e of the diluen t can effect the extr a c tion of me t al ions, and in Table * is sho'n this influenc e on the sep a r a tio n of rare eart h s , in this cas e 5a Pr -$*., 'ith %li,uat ))$. Polarity incre a s e s in the series from tolue n e throu g h to butyl ace t a t e . Ta l e ) 6 1nfluenc e of :iluent s on the Extraction of 8are Earths ?sing %li,uat ))$. :iluent Toluen e Xylene 4ctan e Std 2ineral Spirits Ethyl eth er 210F 0utyl acet a t e "odifiers The modifiers mus t also be inert to the syst e m , soluble in the diluent, and insoluble in the a,u e o u s pha s e . The conc e n t r a ti o n of a modifier gen e r ally rang e s up to "< 'eight per cent of the diluen t. The main function of the modifier is to insur e that the extr ac t e d me t al specie s 'ill rem ain soluble in the diluen t and not caus e a third phas e or emulsion forma tio n. 2odifiers that hav e be e n mos t com m o nly us ed includ e tributyl phos p h a t e , and alcohols such as capryl alcohol, 3 ethylh e x a n ol, isodec a n ol, and tridec yl alcohol. Som e of thes e modifiers are listed in Table $ . 2odifiers pres e n t in a solven t can also affect the extr a c tiv e the syst e m . -;igure 3$.. %lso, the stripping char a c t e ris tics can be alter e d by choice of modifier, as is sho'n in ;igure 'ell, scrub bin g is affect e d by modifiers, as is sho' n in Table Ta l e - Som e 2odifiers 2odifiers 3 ethylh e x a n ol isodec a n ol a Tri n butyl phos p h a t e b
a

Extraction W 3C 3= "D "D "= # =

Sep ar a tio n ;actor 5aEPr 3.C 3.D 3.< 3.$ ".$ ".3 ".=

prop er ti e s of of a solven t 3C -$=.. %s C -$$..

S.>. <.D) = <.D= < <.#C )

0oiling Point ; )$* =3D )*3

;lash Point ;, -T4C. "D* 33< )D<

a %shland Che mic als

b Cana d a Colors 5td

;igure 33 $@ E!!e 9 t o! Mo;i!i er s on t< e E8tra 9 t i o n Usin 5 %2EH&A

o! Rare Eart< s

(i5ur e 2.6 Effect of 2odifier on the Stripping of 8are Earth s from :3E+P% .

Ta l e . 6 Effect of 2odifier on the Scrubbin g of a "* vol W :3E+P% Solven t Cont aining Cobalt and 7ickel. -%@4 *@". Extract, gE5 Solution Co-74 ) . 3 3< gE5 Co -%. 2odifier 1sodec a n ol * volW Co % 3<.D 3".$ 33.= 0 CoS4 = 3C gE5 Co -0. Co-74 ) . 3 3$ gE5 Co -C. T0P * vol W "$.< "$." "$.< C T0P * vol W "$.3 "$.) "$.3 <.3 <." <.<D " 3 ) <." <.<= <.<) " 3 ) 3.< ".* ".= " 3 ) 7i 7umb e r of Cont ac t s

%@ 0,C@

4riginal extr a c t cont ain e d D.= and =.* gE5, Co and 7i, resp e c tiv ely. 4riginal extr a c t cont ain e d "3.# and ).D.gE5, Co and 7i, resp e c tiv ely.

Summary Extract a n t s The gen e r al re,uir e m e n t s for an extr a c t a n t for use in met allurgic al solven t extr a c tion proce s sin g are that it has the follo'ing positive char a c t e ris tics@ -i. -ii. -iii. -iv. -v. -vi. -vii. -viii. -ix. -x. :iluent s >ener al re,uir e m e n t s for a diluen t are that it@ -i. -ii. -iii. -iv. -v. be mut u ally miscible 'ith extr a c t a n t and diluent, hav e high solve nc y for the met al specie s to be extr a c t e d , hav e lo' volatility, lo' toxicity and high flash point, be insoluble in the a,u e o u s pha s e , the optimu m aro m a tic cont e n t for extr a c t e d species solubili&ation and maxi m u m rate of coale s c e n c e , -vi. naph t h e n e s and paraffins comp o n e n t s may hav e to be consid er e d for optimu m che mic al sep a r a tio n s as 'ell as phas e sep a r a tio n rate s / -vii. hav e lo' surfac e tension/ and -viii. be che a p and readily available. 2odifiers The addition of a modifier to a solven t syst e m is to@ -i. incre a s e -ii. incre a s e solven t phas e , -iii. decr e a s e phas e , -iv. decr e a s e -v. improv e the mut u al solubility of extr a c t a n t an diluent, the solubility of extr ac t e d met al species in the or elimina t e emulsion tend e n ci e s in the orga nic relativ ely inexp e n siv e very lo' solubility in the a,u e o u s phas e good stability over long time periods no emulsion forming ten d e n ci e s good coale s cing char a c t e ris tics high me t al loading cap a city rea dily stripp e d of load e d met al non flam m a b l e , non volatile and non toxic highly soluble in available diluent s good extr a c tion kinetics

or elimina t e crud form a tio n in the syst e m , stripping char a c t e ris tics of the load e d solve n t.

SECTION III PROCESS DESI.N

Introd7ction There are ma n y asp e c t s to be consid e r e d in the design of the solven t extr a c tion proce s s , and includ e the follo'ing import a n t are a s @ X X X X X Che mis tr y 2ass transf er E,uip m e n t Econo mics Environ m e n t a l and Solvent s 5osses misting? crud Extracta n t s < )odifiers< 1iluent s 1ispersion and Coalesc e n c e Selection and =peration Capital > =perating Costs Solu.le? entrain e d? evap?

%ll impac t on the possibility of the succ e s sful design, and if som e are partially ignor e d then proble m s in the plant oper a tio n can be anticip a t e d . The time re,uir e d to dev elo p a specific flo'sh e e t 'ill dep e n d on@ X X X Experien c e of the res e a r c h e r s 1nform a tio n in the literat u r e Plant exp erie n c e of similar oper a tio n s

Chemistr6 Extractants The che mis tr y of the proce s s has alre a d y bee n ade , u a t e l y describ e d , 'ith various extr ac t a n t s availabl e, select e d from the class e s of comp o u n d s accordin g to their extr a c tion reaction s@ X X X X Cationic Chelatin g %nionic Solvating

Thus kno'led g e of the met al to be extr a c t e d as to its stat e in solution, as 'ell as the anion and p+, can provid e the early inform a tio n nec e s s a r y to mak e the initial selection as to the possible class of extr a c t a n t s that re,uir e evalu a tio n. "odifiers 7ot all syst e m s re,uir e a modifier 'hich is add e d to improv e the rate of phas e sep a r a tio n, immpro v e the solubility of the extr ac t e d met al comple x in the orga nic phas e , and to decr e a s e emulsion s and solven t entr ain m e n t loss es . 2odifiers are not as eas y to select and a (udicious choice has to be ma d e to select for evalu a tio n. +o'ev er, the phos p h o r u s bas e d extr a c t a n t s usu ally perfor m bes t 'ith T0P as the

modifier, 'hile the anionic extr ac t a n t s such as the amin e s are improv e d 'ith the addition of a long chain e d alcohol, such as tri dec a n ol. Chelatin g extr a c t a n t s usu ally hav e the modifier add e d by the ma n uf a c t u r e r , and may consist of nonylp h e n ol. Solvating extr ac t a n t s do not re,uir e a modifier addition. )iluents %s discus s e d earlier, the proce s s can be influenc e d in the extr a c tion and in the discrimin a tion over impurities by the choice of the diluen t. The che mic al comp o sition of the diluent is ther efor e import a n t , such as the aro m a ticity, par affins, and nap h t h e n e s cont e n t , as 'ell as the solvenc y par a m e t e r . 1t is also usu al, and good practic e, to select a diluen t 'ith a high flash point abov e "$< ;. Physical prop er ti e s such as the viscosity, and den sity relative to the a,u e o u s feed solution are also import a n t . "ass Trans$er Dis0ersion and Coalesence

The physical asp e c t s of solve n t extr ac tio n are prima rily conc er n e d 'ith@ X X X The disper sion of the t'o phas e s in mixing, the type of drople t forma tio n, The rate and comple t e n e s s of coales e n c e . cont a c tin g

Thes e are import a n t asp e c t s in the choice of suita ble e,uip m e n t and in the design and oper a tio n of the plant.

The rat e of mas s transf er is a function, amo n g s t other variable s , of the drop si&e distribution or interfacial are a bet' e e n the pha s e s . The drop si&e is gover n e d by@ X X X %gitation and typ e of cond uc t o r, surfac e tension, densities of the t'o pha s e s .

?p to a point, the smaller the drople t, the gre a t e r the rat e mas s tran sf e r. The effect of mixing on throu g h p u t and perfor m a n c e -disp er sion band dapt h. is sho' n in ;igure 3D.

(i5ur e 23 6 Effect of variation of mixer 7 ) : 3 on settler disper sion band dept h. 0asis@ %,ueo u s phas e <.<* gE5 Cu 3H / p+ ".* 4rganic pha s e *W 51X $=7 in Shellsol T 8ation of 4@% "@" mixe d pha s e flo'Eunit settler are a ,

X axis is expr e s s e d as@ tot al >%5E217E;T 3 o 7) : 3 *< a,u e o u s continu o u s 2 7) : 3 3< a,u e o u s continu o u s 3 7) : 3 )< a,u e o u s continuo u s 4 7) : 3 )< orga nic continuo u s

% proce d u r e has be e n report e d for using dat a on kinetics of mas s transf er to esti m a t e 2urphr e e stag e efficiencie s in continuo u s count e r curre n t mixer settlers so that the num b e r of real cont a c tin g sta g e s can be calculat e d for a 'ide rang e of oper a tin g conditions -C.. Exten siv e test 'ork can thus be minimi&e d by using a limite d set of statis tic ally design e d exp eri m e n t s to det er mi n e the effect on kinetics of mas s transf er of the ma(or oper a tin g variabl e s . 1n ;igure 3= are sho'n the notice a bl e effect on the incre a s e in the rate coefficient s as the stirring spe e d is incre a s e d in a Felex copp er sulph a t e syst e m . The disper sion of the solven t res ult e d in poor er kinetics tha n disp ersion of the a,u e o u s phas e . There 'as little effect on the kinetics due to chan g e in phas e ratios. :ata 'as also pres e n t e d for the effects on sedim e n t a t i o n and coale s c e n c e .

(i5ur e 2* 6 Effect of %gitation and :ispers e d Phas e on Finetics

Coupled 'ith incre a sin g disper sio n ho' ev e r is incre a s e d coale s c e n c e time re,uire d, and ther efor e the settler si&e is affect e d . %lso as the si&e of the droplet s of the disper s e d phas e is incre a s e d , the drople t s beh a v e mor e and mor e as rigid sph er e s , and the rate of ma s s transf er decr e a s e s . Thus kinetics, along 'ith the prop e r disp er sio n and coale s c e n c e , 'ill influenc e the choice of cont a c tin g e,uip m e n t . 1n addition to drop si&e affecting coales c e n c e , ther e are oth er factors@ X X X X X X X surfac e active ag e n t s , te m p e r a t u r e , viscosity, density, pres e n c e of solids, 'etting ma t e ri als 'ithin the cont a c t o r, phas e sep a r a tio n e,uip m e n t to pro mo t e coale s c e n c e rat e.

Phas e disen g a g e m e n t , or coales c e n c e , occurs in t'o main sta g e s . There is the prima r y bre ak time, 'hich relat e s to the settler are a re,uire d/ and the secon d a r y bre ak time 'hich relat e s to the amo u n t of solven t that may be lost by entr ain m e n t in the a,u e o u s pha s e . The coale s c e n c e can be consid e r e d to occur over * stag e s @ X appro a c h of a drop to' ar d s the interfac e , 'hich caus e s both drop and interfac e defor m a tio n/ X da m p e d oscillation at the drop ne ar the interfac e / X forma tio n of a film of the continu o u s phas e bet' e e n the drop and its bulk -discon tinu o u s . phas e / X drain a g e of the film, its ruptur e and remov al, 'ith the initiation of the proc e s s of coales c e n c e / X transf er of the cont e n t s of the drop into its bulk pha s e . 1t is gen e r ally acce p t e d that stag e s -i. and -ii. are very fast, and that -iii. throu g h -v. cons titu t e the time of coale s c e n c e . Step -v. is report e d to occur in <.<$ to <.<D seco n d s -3., thus stag e s -iii. and -iv. repr e s e n t the rate det e r mi nin g step s . This is partially sho'n in ;igure )<. 1n ;igure )" is sho'n the effect of drople t forma tio n and coales c e n c e in a puls e d column 'her e the plat e mat e ri al surfac e s are varied.

;igure )<

Som e of the various sta g e s from mixing disen g a g e m e n t of t'o immiscible li,uids -=.

to

phas e

(i5ur e 2) 6 Effect of Plate 2aterial on 0ubbles and Coalesc e n c e .

E97i0ment The over all econo mic s mus t be consid er e d 'ith res p e c t to the typ e of e,uip m e n t to suit particular condition s of@ X X X X X X X X throu g h p u t , solution and solven t typ e, kinetics and e,uilibriu m, stag e s , disper sion and coales c e n c e , solven t loss e s, corrosion, available are a , etc.

E,uip m e n t has bee n alre a d y describ e d, but in brief, consists of sta g e 'is e and differe n ti al cont a c t o r s in 'hich the flo's of orga nic and a,u e o u s are running count e r c u rr e n t to one anot h e r. 2ixers settler s hav e be e n the mos t com m o n of the stag e 'is e cont a c t o r s , 'hich also includ e the in line mixers. +o'ev er ther e are also ma n y differe n ti al cont a c t o r s , mos tly of agita t e d colum n design, 'hich are beco mi n g of inter e s t. Thes e includ e sieve plat e puls e column s , 2ixco column s , 8otating disk, Scheib el, Fuhni, etc., as 'ell as the centrifug al cont a c t o r s such as the Podbielniak centrifug e s , and also the 8T5 0ucket cont a c t o r. % classification of cont a c t o r s is given in ;igure )3.

(i5ur e 2- 6 Classification of Contac t or s

The ma(or emp h a s is in the design and optimi&a tion has bee n to incre a s e the throu g h p u t 'hile maint aining efficiency, and also to incre a s e the efficiency 'ithou t reduc tion in throu g h p u t . There is not one single cont a c t o r that is bes t for all extr ac tio n situa tion s . The physical and che mic al prop er ti e s of the syst e m , as 'ell as the desire d produc t specification s , are factors in the ass e s s m e n t of a nu mb e r of cont a c t o r s and the subs e , u e n t choice of the bes t cont a c t o r to suit that particular proc e s s . % comp a ris o n of cont a c t o r s is valid only und er the sa m e identical proc e s s conditions of phas e ratio, te m p e r a t u r e , solution comp o sition, etc. Economics The follo'ing may singly, or in combin a tio n, contribu t e to the decision on the possible use of solve n t extr ac tio n@ X X X the conce n t r a tio n of me t al s in solution, the value of the met al being recov er e d , flo' throu g h p u t .

The econ o mic consid er a tio n s may be divided into@ X X Capital inves t m e n t s 4per a tin g costs

Capital costs are primarily relat e d to the si&e of the e,uip m e n t nec e s s a r y for a given throu g h p u t . ?sually the building re,uire d to hous e the proce s s is an import a n t cost factor, as 'ell as the solven t invent o r y. 4per a tin g costs ma y be divided into sev er al are a s @ X X X X X X X Prep a r a tio n of the feed solution Pretr e a t m e n t of the solven t may be re,uire d Scrubbin g of und e sir a bl e impurities Stripping costs vary from one proc e s s to anot h e r Solven t loss e s 5abour and maint e n a n c e 5osses of the produc t in the raffinat e

4ther factors affecting the proce s s costs includ e the follo'ing@ X X X X X Solven t conce n t r a ti o n 6iscosity %gitation -she a r. Phas e continuity 7umb e r of stag e s

;lo' ratio

Desi*n o$ the Process The design of the proce s s 'ill be dep e n d e n t upon the satisfying cert ain criteria, 'hich 'ill of cours e reflect on the choice of a hydro m e t a llur g y option. Som e of the ,ue s tion s that might be aske d includ e@ X X X X X X X X 2etal or met als to be recov e r e d 1mpurities :esired purity Possible purification proce s s e s s Environ m e n t a l cons tr ain t s Energy re,uire m e n t s Possible by produc t recov e r y 4ver all capital and oper a tin g costs

6arious hydro m e t a llur g y rout e s are poss bl e options@ solven t extr a c tion, ion exch a n g e , cem e n t a ti o n, electrolys e s , revers e os mo sis, etc. Thes e may be singly or in cert ain combin a tio n s The solven t extr a c tion proce s s has bee n utili&ed to ben efit in ma n y situa tion s , including tre a t m e n t of he a p leach solutions/ integr a ti n g into an alre a d y existing plant oper a tio n/ and tre a t m e n t of effluen t s for by produc t s or to me e t environ m e n t a l stan d a r d s . There can be ma n y step s in the proc e s s dev elo p m e n t , and the ma(or are a s includ e@ X X X X X selection of the extr ac t a n t , diluen t, modifier e,uilibria and kinetic dat a stag e s re,uire d scrub and stripping re,uire m e n t s phas e continuity

The time re,uir e d for the dev elo p m e n t , optimi&a tion, and the decision to proce e d to the next pha s e , such as the mini circuit, pilot plant and subs e , u e n t plant design and scale up 'ill dep e n d on factors such as the relativ e exp erie n c e of the res e a r c h tea m , the facilities, backgro u n d inform a tio n in the litera t u r e , and the possible inform a tio n of any oper a tin g plants . 4ne of the appro a c h e s that ma y be of use, and 'hich has bee n use d by other s 'ith succe s s is the PE8T -progr a m , evalu a tio n and revie' tech ni, u e . in 'hich sev er al eve n t s may be perfor m e d simult a n e o u s l y in order to arrive at the flo'sh e e t design in a limited time. Scre e nin g tes ts on the possible extr ac t a n t s are initially perfor m e d , usu ally in sep ar a t o r y funn els. Thes e early shak e outs are often perfor m e d 'ith an exce s s of reag e n t and for a cont a c t time prob a bly in

exce s s of the final design, such as using *W "<W extr ac t a n t in cont a c t 'ith the solution at a phas e ratio of "@" for a * minut e cont a c t time. Som e of the me a s u r e m e n t s and dat a pres e n t a tio n might includ e@ X X X Eh p+ E,uilibriu m p+/ free acid Extraction efficiency, 'hich ma y be me a s u r e d by the extr ac tio n or distribution coefficient
E Co = 4 %

'her e

is

the

an alytic al

X X X X X X X

conc e n t r a ti o n in the orga nic phas e and % is the conce n t r a tio n in the a,u e o u s phas e / W extr ac tio n/ p+ J value s -p+ at 'hich *<W of the me t al is extr a c t e d .
Co :iscrimin a tio n over impurities, or the sep a r a tio n factor, eg S; I E 7i :istribution Curve 2cCab e Thiele diagr a m Phas e sep a r a tio n time s -prima r y and secon d a r y bre ak. 8ate s of ma s s transf er as affecting efficiency and discrimin a tio n

Prior to the extr a c tion test s it ma y be nec e s s a r y, and prob a bly advis a bl e, to tre a t the solven t mixtur e 'ith a 'as h solution. This is to remov e any cont a mi n a n t s that may, and are often, be pres e n t in the solven t. Thes e cont a mi n a n t s may be the result of produc t s from the ma n uf a c t u r e or other subs t a n c e s . The efficiency of the proce s s ma y be very dep e n d e n t upon the phas e continuity relativ e to the cons titu e n t s and amo u n t s in the feed, the type of cont a c t o r and its oper a tio n, such as amo u n t of she a r. This applies to each of the sta g e s in the solven t extr ac tio n proce s s . 0eca u s e the solven t extr a c tion proce s s ob(ectiv e s includ e the sep a r a tio n, conc e n t r a ti o n, and purification of me t al s, it is really imper a tiv e that the che mic al syst e m is design e d to oper a t e in the physical syst e m in such a ma n n e r that the s e ob(ective s are att ain e d . To optimi&e the proce s s , the follo'ing are som e gen e r al rules that can be applied if the ob(ectiv e s are to be me t@ X Perfor m only limite d tes ts on synt h e tic solution s, and 'ork on the real leach li,uors as soon as possible for ther e ma y be serious differe n c e s in not only the physical but also the che mic al prop e r ti e s as affecting optimu m perfor m a n c e . 4per a t e as close to satur a tio n as possible. :iluent selection can be almos t as import a n t as the selection of the extr a c t a n t .

X X

1ncre a s e d he a t usu ally provide s enh a n c e d kinetics, improv e d discrimin a tio n, and improv e d phas e sep a r a tio n rate s , but also incre a s e d solve n t loss e s . % specific acidity or an e,uilibriu m p+ may hav e to be maint ain e d . Phas e continuity is usu ally run for the pha s e that the met al is being transf err e d to/ the rate of phas e sep a r a tio n can also be affect e d , so the choice has to be bas e d on both criteria. 1ncorpor a t e a scrub sta g e bet' e e n extr ac tio n and stripping to remo v e the entr ain e d a,u e o u s feed 'hich 'ould oth er'is e carry over into the prod uc t, e.g. the tankh o u s e . Establish if a selective impurities. scrub -strip. can be used to remo v e

X X

X X X

?se a purification scrub for maxi m u m purity. 2ake use of kinetics, and ther efor e design the mixer for the rete n tio n time de m a n d e d of the che mic al tran sf e r proc e s s / overd e sig n can only lead to incre a s e d extr a c tion of impurities. The selection of the particular design of the cont a c t o r, and its oper a tio n, should be bas e d on the particular physic al char a c t e ris tics of the specific leach feed solution, and not bas e d nec e s s a rily on the perfor m a n c e of anot h e r plant.

(i5ur e 2. 6 +ypoth e tic al 2cCabe Thiele :iagra m .

(i5ur e 28 6 Some e,uilibria involve d in the extr a c tion of a met al.

SECTION I% -ENCH TESTIN. CONTIN!O!S TESTIN. PI OT P ANT P ANT

Scale:708 -ench Contin7o7s to Pilot Plant 'ench Continuous ;ollo'ing the test s that hav e no' indicat e d a possible flo'sh e e t , the next stag e is to run a small continu o u s count e r c u rr e n t flo' syst e m . The small scale tes ts are usu ally in the order of up to a fe' "<< m5Emin in total flo's. There are various typ e s of cont a c t o r s that might be adv a n t a g e o u s l y evalu a t e d during this sta g e in order to provide an idea of the possible design type s that could be consid e r e d in any subs e , u e n t pilot plant. Thes e includ e various typ e s of mixer settler s, in line mixers, various colum n s and centrifug e s . %ll hav e adv a n t a g e s and disadv a n t a g e s , but one or mor e may prove mor e viable, tech nic ally and econ o mic ally, tha n oth er cont a c t o r s for that particular solution. The adv a n t a g e s of running a continu o u s syst e m includ e@ X X X X X 6erify conce p t u a l flo'sh e e t and modify and optimi&e :eter mi n e possible pha s e sep a r a tio n proble m s 4btain a rough me a s u r e of anticip a t e d solven t loss e s , eve n at the lo' flo's us ed Exa min e phas e continuity effect s Training of the oper a t o r s in the proce s s

The sub(ect of disp er sio n and coales c e n c e has alre a d y be e n cover e d . There are som e eas y test s that can be perfor m e d to est a blis h the effect of the continuo u s phas e on the settler re,uire m e n t s . ?sing a single stag e mixer box att a c h e d to a dee p settler that cont ains mov a bl e plat e s that can ther efor e chan g e the settler lengt h, good design dat a can be obt ain e d . Such test s also can indicat e 'het h e r a sta bl e emulsion can be anticip a t e d . % decision to ter min a t e the running of the circuit can includ e, bas e d on the continuo u s circuit, the follo'ing@ X X X Poor extr ac tio nE s e p a r a ti o n of met als Poor pha s e sep ar a tio n, 'ith high entr ain m e n t loss e s Poor scrub bin g and stripping

+o'ev er this is not nece s s a rily the ter min a tio n of the pro(ect. 4ften the proble m s can be take n back to the labor a t or y and improv e m e n t s ma d e such that furth e r continu o u s small scale testin g 'ill re com m e n c e .

%ssumin g that the small scale continuo u s tes ts hav e prove n succ e s sful, the n the comp a n y may decid e on the scale up to a pilot plant to provid e valua bl e inform a tio n on the ultima t e plant design.

Pilot Plant The si&e of a pilot plant has al'ays be e n a point for discus sion. ;or som e , a large pilot plant is the only 'ay to obt ain all the nece s s a r y inform a tio n, 'hich can be take n 'ith confide nc e . 4ther oper a t o r s 'ould rath e r hav e a small pilot plant. 4ften the reas o n or ration al e is the relative costs. 4r it may be due to the fact that perh a p s ther e is only a limited supply of the ore, possibly as drill cores, so this nec e s sit a t e s a small pilot plant. Thus the flo's to a pilot plant can rang e from a fe' liters per minut e up to sev er al hundr e d or more liters per minut e . %lso, the cost can vary from a pilot plant cons tr uc t e d from inexp e n siv e mat e ri als on the site by the comp a n y, to an extr e m e l y exp e n siv e pilot facility that ma y hav e bee n design e d and cons tr uc t e d from the bes t ma t e ri als and 'ith the Rbes tR engin e e r e d cont a c t o r, and installed by an engin e e rin g comp a n y. Some pilot plant s are si&ed bas e d on a specific fraction of the ultima t e plant flo', e.g. "E*<. Thus ther e are no set rules to the si&e and design of plot plants . There can gover n e d achieving ob(ectiv e s , X X X X X be ma n y ob(ectiv e s in running a pilot plant. Som e 'ill be by the de m a n d s of the comp a n y, and oth er s are set in the econo mic ally succ e s sful oper a tio n. Som e of thes e in no particular order of import a n c e , includ e the follo'ing@ as

verification of the benc h dat a and the conc e p t u al flo'sh e e t produc e d by the small scale continuo u s circuit/ obt ain final purified produc t s analys e s / for exa mi n a tio n

and specification

obt ain dat a for exp ec t e d solven t loss e s/ evalu a t e the effect of pha s e continuity on perfor m a n c e as 'ell on the physical oper a tio n/ evalu a t e the det er mi n e proble m s / the che mic al

perfor m a n c e of the extr a c t a n t 'ith recycle, to any possible degr a d a tio n loss e s or poisoning

X X

evalu a t e unex p e c t e d proble m s that ma y occur, and det er mi n e the caus e so that they are not rep e a t e d in the plant/ provid e sufficient dat a for the econ o mic and tech nic al feasibility calculation s and for the scale up design/

det er mi n e the volu m e ratios, and conc e n t r a ti o n s of me t al s and anions, re,uir e d for any recycle stre a m s or blee d stre a m s re,uiring dispos al or furth e r tre a t m e n t / e valua t e and comp a r e the cont a c t o r possibilities/ train pers o n n el/ and identify possible are a s 'her e furth e r optimi&a tio n is re,uir e d befor e scale up. relative perfor m a n c e of altern a t e

X X X

The com m o n conc er n s in scale up to pilot plant oper a tio n includ e@ X X X X X Plant 4nce the proc e s s has be e n pilote d, and the plant put on stre a m , the plant oper a tio n al efficiency may often be less tha n the design. This 'ill be due to various proble m s , som e of 'hich should hav e be e n discov er e d in the pilot plant if it had be e n run sufficiently long. Thes e proble m s includ e the follo'ing@ X X X X X X X X X X Emulsions and cruds Coalesc e n c e ;ouling -bact e ri a, scale. 1nterfac e control -crud, etc. Phas e inversion Plant control Treat m e n t of 'ast e stre a m s Product ,uality control Solven t loss e s -solubility, entr ain m e n t , degr a d a tio n Solven t recov e r y circuit control -e.g. p+, flo's, interfac e , phas e continuity./ solven t loss e s and solve n t degr a d a ti o n / cruds and stable perfor m a n c e / emulsions 'hich 'ould decr e a s e circuit 'ith

oper a tio n of small e,uip m e n t 'hich can provide proble m s pu mp s , lines blocking, ineffectiv e instru m e n t a ti o n / produc tion of off specification produc t s .

cruds,

eva p o r a tio n,

and

SECTION % E;!IP"ENT

Continuo u s cont a c tin g e,uip m e n t for solve n t extr ac tio n can be divide d into t'o ma(or are a s , accordin g to 'het h e r their mod e of oper a tio n is stag e 'is e or differe n ti al - ;igure 3# .. 2ixer settlers and the 5ightning, Fenics and Sul&er in line mixers typify the stag e 'is e cont a c t o r s . 1n thes e count e r c u r r e n t cont a c t o r s , the a,u e o u s and the orga nic phas e are mixe d and the n sep ar a t e d in a large settling are a befor e the next stag e of mixing. Count e r c u r r e n t differe n ti al cont a c t o r s , such as centrifug e s and various typ e s of column s , are mor e comp a c t in that they re,uire less groun d are a tha n mixer settlers .

(i5ur e 29 6 Cont ac t o r Classification.

Contac t or s , in addition to being eith er sta g e 'is e or differe n ti al, can be furth e r subdivide d into non agit a t e d and agita t e d dep e n di n g on the met h o d used for mixing the phas e s and producin g the count e r c u rr e n t flo'. The simple s t cont a c t o r s such as spra y, packe d , or perfora t e d plat e column s achiev e both the mixing and count e r c u r r e n t flo' by me a n s of. the gravity differe n c e bet' e e n the t'o phas e s . 1n agit a t e d cont a c t o r s such as the Scheib el, 8eciproc a tin g Plate, and Sieve Plate Pulse, mec h a nic al agit a tion is introd uc e d but gravity differe n c e s still prod uc e count e r c u r r e n t flo'. To cons e rv e plant spac e , and for large throu g h p u t 'ith short cont a c t time, centrifug al cont a c t o r s are us ed 'her e possible. The rea d e r can refer to revie' s on the sub(ect -" ""..

(i5ur e 30 6 2ixer Settler :iagra m .

(i5ur e 3$ 6 :avy Pump mix and 0affled 2ixer.

(i5ur e 32 6 Frebs 2ixer Settler.

(i5ur e 33 6 :avy Combin e d 2ixer Settler.

(i5ur e 3* 6 6S; tubular SP184F stirrer.

(i5ur e 3) 6 6S; mixer settler.

(i5ur e 3- @ 5ightnin ;irst and Secon d Stag e 2ixers #

(i5ur e 3. 6 Fenics Static 2ixer@ -"E3 inch dia m e t e r ..

(i5ur e 38 6 7on agita t e d Column s .

(i5ur e 39 6 8eciporc a tin g Plate Column s .

(i5ur e *0 6 Scheib el Column.

(i5ur e *$ 6 2ixco Column.

(i5ur e *2 6 8otating :isc Cont ac t o r 1nterfac e in Top Comp a r t m e n t .

(i5ur e *3 6 Fuhni 1ntern als and ;lo' Patt e r n s .

(i5ur e ** 6 %8: Extract or.

(i5ur e *) 6 Uiehl Extractor.

(i5ur e *- 6 Sieve Plate Pulse Column.

(i5ur e *. 6 4per a tin g 8egions of a Pulse Column.

(i5ur e *8 6 0ate m a n Plate 9 :onut Pulsed Column.

(i5ur e *9 6 >raes s e r Cont ac t or -" ft. dia m. by ) ft long..

(i5ur e )0 6 Podielniak Centrifug al Contac t or.

Ta l e 8 6 E,uip m e n t Perfor m a n c e .
Mi8 er Se t t l e r s "on- A5it a t e ; %i!! e r e n t i a l A5it a t e ; %i!! er e n t i a l Centri! u 5 a l

%dvant a g e s

:isadv a n t a g e s

>ood cont a c tin g of phas e s . +andle 'ide rang e of flo' ratio -'ith recycle.. 5o' he a d roo m. +igh efficiency. 2any stag e s . 8eliable scale up. 5o' cost. 5o' maint e n a n c e . 5arge hold up. +igh po' er costs +igh solven t invent o r y. 5arge floor spac e. 1nters t a g e pu mpin g may be nec e s s a r y.

5o' initial cost. 5o' oper a tin g cost. Simples t constru c tion.

>ood disp er sio n. 8eas o n a bl e cost. 2any stag e s possible. 8elatively eas y scale up

+andle lo' gravity differe n c e . 5o' hold up volu m e . Short hold up time. Small spac e re,uire m e n t . Small invent o r y of solven t. +igh initial cost. +igh oper a tin g cost. +igh maint e n a n c e . 5imited nu mb e r of sta g e s in single units, altho u g h som e units hav e 3< sta g e s .

5imited throu g h p u t 'ith small gravity differe n c e . Canno t han dl e 'ide flo' ratio. +igh he a d r o o m . Some ti m e s lo' efficiency. :ifficult scale up.

5imited throu g h p u t 'ith small gravity differe n c e . Cannot handle emulsifying syst e m s . Cannot handle high flo' ratio. !ill not al'ays handle emulsifying syst e m s , exce p t perh a p s puls e column s .

SECTION %I

RECO%ERY O# COPPER

Rea*ent Develo0ment There hav e bee n consid er a bl e dev elo p m e n t s in extr ac t a n t s in the me t al s extr a c tion tech n olo g y, but the gre a t e s t has bee n in the copp e r indus tr y. This has res ult e d in ma n y extr ac t a n t s , each 'ith feat ur e s that can be comp a ti bl e 'ith a 'ide rang e of solution typ e s . The follo'ing on the history of the dev elop m e n t s has be e n abs tr a c t e d from cours e note s by +iskey and 2uir, "##= pres e n t e d at the ?niversities of 2elbourn e and 2urdoch by 8itcey, Stev e n s , 2uir and +iskey -"D.. 5i,uid ion exch a n g e -51X. rea g e n t s 'ere dev elop e d and first introd uc e d by >ener al 2ills in "#$), 'ith 51X $), an alph a hydrox y oxime for the extr a c tion of copp e r. +o'ev er the extr ac tio n p+ for Cu 'as not sufficiently lo' to extr a c t copp e r from dilute sulphuric acid dum p leach li,uors cont ainin g abou t " 3g CuE5 and 3 *g ;eE5 at p+ 3. The subs e , u e n t first succ e s sful rea g e n t s -51X $=, 51X $*. had a ketosi m e struct u r e -'her e %IC $ + * . 'ith slightly differe n t alkyl subs titu e n t s , but prove d to be kinetically slo' to extr ac t copp e r. +o'ev er, addition of only "W of the 51X $) -*,D diethyl C hydrox y $ dod ec a n o n e oxime. 'as found to cat alys e the rate of copp e r extr a c tion. This mixtur e , kno'n as 51X $=7, 'as 'idely use d, begin nin g 'ith the first plant in "#$#, and throu g h the "#C<Ts. 4ther rea g e n t s 'ere dev elop e d and improv e m e n t s ma d e in plant perfor m a n c e throu g h the ne' rea g e n t dev elo p m e n t s . The struct u r e s of the s e rea g e n t s sho'n the struct u r e s of oth er gen e r al struct u r e of the seco n d for copp er extr ac tio n is sho'n in are sho'n in ;igure $<. 1n ;igure $" are first gen e r a tio n copp er rea g e n t s . The gen e r a tio n hydrox yp h e n yl oxime s used ;igure $3.

Shell then introdu c e d a modified ketoxi m e -'her e %IC+ ) ., 'hich exhibite d fast er kinetics and nee d e d no addition of 51X $). This rea g e n t , first kno'n as S2E *3# or S2E *)<, is no' a 51X prod uc t und e r the na m e of 51X D=. 1t is proving to be an excellen t extr a c t a n t for nickel -as 'ell as Un 9 Cu. from am m o ni a c al solution s. Table "= sho's a comp a ris o n of ketoxi m e s and aldoxim e prop er ti e s . Subs e , u e n tl y, %corga 1C1 introd uc e d salicyaldoxi m e s -'her e %I+ ., 'hich sho' e d eve n fast er kinetics and gre a t e r copp e r extr a c tiv e stre n g t h . 2odifiers such as nonylph e n ol or tridec a n ol had to be add e d to allo' the copp e r to be effectiv ely strippp e d und er stron g acid conditions. The %corga P*<<< series of rea g e n t s cont ain e d various ratios of modifier, dep e n di n g upon the li,uor to be tre a t e d .

Ta l e 9 6 Comp a ris o n of Fetoxim e %ldoxim e perfor m a n c e prop e r ti e s &ro> e r t : 1eto 8i 7 e 2oder a t e Al;o8i 7 e

Extractiv e 6ery stron g stre n g t h Stripp a bility 6ery good 7ot good CuE;e selectivity Excellen t Excellent Copper kinetics ;ast 6ery fast Phas e sep a r a tio n 6ery good 6ery good Stability 6ery good 6ery good Crud gen e r a tio n 5o' 6ariableV V:ue to modifier use d to pro mo t e stripping

(i5ur e -06 Structur e s of early hydroxy oxime copp e r extr a c t a n t s

(i5ur e -$6 Struct ur e s of other first gen e r a tio n copp e r extr a c t a n t s

(i5ur e -26 >ener al struct ur e of hydrox yp h e n yl oxi m e s 1n Table "3 are sho'n som e tren d s in rea g e n t prop er ti e s of the rea g e n t s . %lthoug h the extr a c tiv e stre n g t h of the mixtur e s is not ,uite as high as the modified salicylaldoxi m e s , it is consid e r a bly gre a t e r than the ketoxi m e s . Copper tran sf e r kinetics are a little slo'er tha n salicylaldoxi m e s , but still very fast. Ta l e $0 @ Trend s in 8eag e n t Proper ti e s Rea 5 e n t &ro> e r t : Extractiv e stre n g t h CuE;e selectivity Finetics Stability Crud gen e r a tio n 6ersatility LI' -) ?$ 9 - ) @ 2oder a t e ;air Slo' Excellent >ood 7ot good ACOR+A ?7i;$9 . 0 A s @ Stron g >ood 6ery fast >ood 2oder a t e >ood MI'TURES ?To; a : @ Tailored Excellent Tailored 6ery good 6ery good Excellent

4ne inter e s tin g feat ur e of thes e mixtur e s is the gre a t e r than exp e c t e d copp e r transf er due to the lo'er than exp e c t e d stripp e d orga nic value. 1t is felt this prop e r t y res ults from the ketoxi m e comp o n e n t of the mixtur e functioning as a modifier for the salicylaldoxi m e comp o n e n t in the strip stag e s of the circuit. The mixtur e s 'ere introd uc e d to the indus tr y in "#D3 and are no' the mos t 'idely use d copp e r extr ac t a n t syst e m in the 'orld.

Since the ketoxim e and salicylaldoxi m e comp o n e n t s can be mixe d in any ratio, a rea g e n t mixtur e can be tailore d to the de m a n d s of almo s t any leach li,uor. 1nde e d, the s e mixtur e s could prov e in time to be a univers al rea g e n t syst e m for acid sulfat e copp er leach solutions since, in mos t insta n c e s , a prop e rly tailore d mixtur e 'ill function both physic ally and che mic ally very 'ell 'ith virtu ally any leach solution of this typ e. The various oxime copp e r extr a c t a n t s available from +enkel -Cognis. Corpor a tion, eith er alone or mixe d, are highly selective for copp e r over iron from almo s t all copp er leach solutions. %s a res ult, minimu m tankho u s e blee d s are re,uire d for iron control. Som e are sho' n in Table "). 1n Table "= are sho'n som e of the com m e r ci al chela tin g -51X and %corga. reag e n t s , sho'ing the modifier addition to the rea g e n t . Ta l e $$ 6 Compo sition of Some +ydroxy 4xime Copper Extract a n t s available from +enkel Corpor a tio n. E8tra 9 t a n t BC a t e 5 o r : 51X D=EFetoxi m e 51X D$<E%ldoxim e 51X #D=E2ixtur e 51X $33ES alicylaldoxi m e Co7 > o s i t i o n % mixtur e of * nonylac e t o p h e n o n e oxime and a small amo u n t of * dode c yls alicylaldoxi m e in keros e n e . Strip 'ith "*<gE5 + 3 S4 = . % mixtur e of * dod e c yis alicylaldo Y i m e and a small amo u n t of * nonylac e t o p h e n o n e oxime in keros e n e . Strip 'ith L 3 3 * g E5 + 3 S< = . %n e,uivolu m e mixtur e of 51X D= and 51X D$<. Strip 'ith "$<gE5 + 3 S4 = . % mixtur e of * dod ec yls alicylaldoxi m e and tridec a n ol in keros e n e . Strip 'ith "C<gE5 + 3 S4 = .

Ta l e $2 @ Com m e r ci ally %vailable Copp er SX 8eag e n t s Rea 5 e n t %corga P*"<< %corga PT*<*< %corga 2*$=< 51X D= 51X #D= 51X $33 51X D$< E8tra 9 t a nt %ldoxime %ldoxime %ldoxime Fetoxim e 2ixture %ldoxime %ldoxime Mo;i!i er 7onylph e n ol Tridec a n ol Ester 7one 7one Tridec a n ol 7one E8tra 9 ti = e Str e n 5 t < Stron g Stron g Stron g 2oder a t e Stron g Stron g 6ery stron g

Solution p+ of the a,u e o u s phas e extr a c tion. Copper leach solutions belo' p+ 3.*. 1n the cas e of oxide re,uir e d to maint ai n the leaching

is very import a n t in copp e r solven t typically cont ain " 3 gE5 Cu and are ores, sufficient acid conce n t r a tio n is reaction. 1n the acid ferric sulfat e

leaching of sulfide ores, lo' p+ provide s the a,u e o u s stability of ferric ion -i.e. ferric hydrolysis occurs bet' e e n p+ 3.* and ).<.. Table "* su m m a ri& e s the typical sulfuric acid leach solutions for various leaching syst e m s . 1t is import a n t that solven t extr ac tio n conditions and perfor m a n c e consist e n t 'ith copp e r leaching and met al recov e r y proce s s e s . Ta l e $3 @ Typical Copper 5each Solutions T:> e :ump 1n situ +eap Thin layer 6at %gitation Cu, 5BL O" ) O" ) ) $ ) "< * *< " $ >H ".3 3.3 ".D 3." ".* 3.3 ".C 3.< ".$ 3.< ".D 3.< be

Copp er extr a c tion as a function of p+ is plott e d for 51X $) and 51X $= in ;igure $). The p+ *< value s are =.D and 3.# for 51X $) and 51X $=7 resp e c tiv ely. 1t is clear that 51X $=7 exhibits bett e r p+ perfor m a n c e -i.e. high er copp e r extr a c tion s at lo'er p+Ts.. +o'ev e r, at p+ 3.* e,uilibriu m copp e r extr ac tio n is only abou t )< W. This 'ould re,uir e a large num b e r of stag e s to achiev e acce p t a bl e levels of copp e r recov er y. p+ *< value s for various early copp er extr a c t a n t s are report e d in Table "$. FE5EX "<< afford e d relativ ely good p+ beh a vio ur on extr ac tio n. +o'ev er, as point e d out by 8itcey and %shbrook -"#., FE5EX "<< had proble m s in stripping. 1t had a ten d e n c y to form salts 'ith acids, since the molec ul e cont ains a tertiary nitrog e n . This 'ould res ult in large amo u n t s of acid being extr a c t e d during stripping.

(i5ur e -3 @ Copper extr a c tion as a function of p+ for first gen e r a tio n SX extr ac t a n t s , 51X $) and 51X $=7. Ta l e $* @ p+ *< value s for first gen e r a tio n Copp er extr ac t a n t s LI' -3 =.D LI' -* ).3 LI' -*" 3.D LI' .0 3.$ 1ele 8 $0 0 3.<

>H )0

Earl6 Co00er O0erations Sulphate Systems Sulphuric acid leachin g has be e n up to the pres e n t , the mos t popular of the leachin g rout e s . 4xide ores are usu ally leach e d 'ith sulph uric acid directly by dum p leachin g or by vat leaching, ?p gradin g of the lo' grad e oxide ores by dum p leaching follo'ed by ce m e n t a t i o n of the copp e r from solution by scrap iron has be e n replac e d by the leachin g solve n t extr a c tion electro'inning rout e 'hich res ults in a high purity produc t at the mill site at reduc e d produc tion costs comp a r e d to previou s practic e. +igh grad e oxide ores, vat leach e d 'ith + 3 S< = , can cont ain, for exa m pl e , 3*g CuE5 and 3*g + 3 S4 = E5, or high er conce n t r a tio n s of both, and are pres e n tly fed directly to electror efining plant s. %dvant a g e s of coupling solven t extr a c tion electro'inning 'ith the lo' cost du mp leaching inste a d of using cem e n t a ti o n , are as follo's -".@

the prod uc tio n of high purity electrolytic copp er rath e r tha n ce m e n t copp e r the purch a s e of scra p iron is elimin a t e d the oper a tin g costs and the capit al inves t m e n t are retur n e d from the elimina tio n of the smelt e r charg e s on cem e n t copp e r the acid re,uire m e n t s for leaching are reduc e d by the amo u n t reg e n e r a t e d in the electro'inning proce s s furth e r acid reduction s are obt ain e d from the elimina tio n of iron from the leach li,uor. %t 0luebird, the acid cons u m p ti o n per poun d of copp e r recov er e d 'as reduc e d by approxi m a t e l y 3Z*lbs from that re,uire d during ce m e n t a t i o n the elimina tio n of hydr a t e d iron sulph a t e from the he a p dum p s of ne' ore, 'hich 'ould, if pres e n t , co precipita t e som e copp e r, coats the ore, and affects the per m e a b ility and ther efor e the leaching rate.

+istorically, the first plant to us e the du mp leaching solven t extr ac tio n electro'inning se, u e n c e for recov er y of copp e r 'as the 8anch e r s 0luebird 2ine at 2iami, %ri&ona -",""., oper a t e d by the 8anch e r s Explora tion and :evelop m e n t Corpor a tio n. Production beg a n in "#$D/ the flo'sh e e t is sho' n sch e m a ti c ally in ;igure $=. 1n this ope n pit copp e r mine -"",<< < tpd., the ore 'as transf err e d to # leaching ponds . The leachin g time 'as abou t "* days in eac h pond, 'ith an accu m ul a tio n leach of approxi m a t e l y ")* days. The P5S from the hea p s gravit a t e d to a stor a g e pond and cont ain e d ".D 3.=g CuE5. ;ollo'ing filtration throu g h diato m a c e o u s eart h to remo v e susp e n d e d solids, 'hich 'ould caus e emulsion, the solution 'as he a t e d to D< < ; by a hea t exch a n g e r , and pu mp e d to a stor a g e tank for feed to solven t extr a c tion. The a,u e o u s feed to the SX 'as at a rat e of "D<< gE mi n in cont a c t 'ith solven t at a flo' of #<<gE min. The solve n t mixtur e consist e d of #.*W 51X $=7 in 7apole u m =C< diluen t. The pha s e ratio of orga nic to a,u e o u s 'as abou t 3.*@". Extraction 'as orga nic continuo u s . % typical extr a c tion diagr a m for a feed solution at )g CuE5 and using CW 51X $=7 is sho'n in ;igure $*. To obtain a final raffinat e of <.=g CuE5, thre e stag e s of mixer settlers 'ere re,uir e d, yielding a load e d solven t of ".)Cg CuE5. The tot al flo' into extr a c tion 'as abou t $<< ?S gEm. 8affinat e from the extr a c tion circuit, cont ainin g abou t 3*<p p m total solven t 'as tre a t e d in flotation cells to remov e entr ain e d solve n t. The tre a t e d raffinat e 'as retur n e d to the du mp leaching pond s. The stripping circuit consist e d of 3 stag e s of mixer settlers , 'her e the copp e r 'as recov e r e d from the load e d solve n t by stripping 'ith spen t electrolyt e cont aining "=<g + 3 S< = E5 and )<g CuE5. The result a n t copp e r sulph a t e solution, at )=g CuE5 'as return e d to the electrolytic cells for recov er y of copp e r. The stripp e d solven t, 'hich is recycle d to the

extr a c tion circuit, cont ain e d abou t <."* g e,uilibriu m diagr a m is sho'n in ;igure $$.

CuE5.

% typical

stripping

(i5ur e -* @ 0luebird 2ine Solven t Extraction and Electro'innin g Plant

(i5ur e -) Typical Copper extr ac tio n e,uilibriu m diagr a m

(i5ur e -- Typical Copper stripping e,uilibriu m diagr a m This first and the design e d solutions Cu circuit 'as a casc a d e design 'her e the P5S 'as pum p e d up lighter solven t flo'ed by gravity. %ll succ e s siv e circuits 'ere for pu mp mix, in 'hich the agita t or 'as design e d to pum p the from stag e to stag e as 'ell as mix the solution s.

The 0agd a d Copp er Comp a n y plant, also in %ri&ona, used a flo'sh e e t similar to the 8anch e r s plant in ma n y res p e c t s -),=.. This seco n d Cu plant 'as again open pit, du mp leaching, and provide d a total of )3<< gE m of solution, at abou t ".=g CuE5, 'hich 'as split into = par allel mixer settler circuits. The solve n t 'as 51X $= in 7apoleu m =C< diluent. The final raffinat e cont ain e d <.3g CuE5 and 'as recycle d to leaching. The first stag e of stripping, 'ith ")<g + 3 S< = E5 'as orga nic continuo u s , 'hile the other ) sta g e s 'ere run a,u e o u s continu o u s . The stripp e d solven t cont ain e d abou t <.3* g CuE5. 8ecycling the strip solution at #<g + 3 S< = E5 result e d in conce n t r a ti n g the copp er to *$gE5, cont aining ")<g free + 3 S< = E5. The rat e of produc tion per day 'as abou t =<,<< <lb of electrolytic copp e r in the tankh o u s e . The flo'sh e e t is sho'n in ;igure $C.

(i5ur e -. @ Sche m a tic layout of the 0agd a d Copp er Comp a n yTs solven t extr a c tion plant The next plant, 7chan g a Consolida t e d Copp er 2ine -7CC2., in Uambi a, 'hich 'ent on stre a m early in "#C=, tre a t e d sulphid e mill tailings for their oxidi&ed copp e r cont e n t , by leachin g 'ith sulphuric acid, follo'ed by SX E!. The SX E! oper a tio n 'as abou t "< time s the si&e of the 0agd a d plant. Sever al alter n a tiv e s 'ere evalu a t e d -*. and althou g h all 'ere econ o mic ally viable, the SX E! rout e 'as chos e n . ;eed solution cont ainin g abou t 3.*g CuE5 at a flo' of abou t "*,<< < gEm 'as fed to the thre e stag e extr a c tion circuit and cont a c t e d 'ith 3<W 51X $*7 at a total flo' of approxi m a t e l y )3,<< < g E m . %fter t'o stag e stripping 'ith deplet e d electrolyt e -)<g CuE5. the feed to electro'inning cont ain e d abou t *<g CuE5. The + 3 S< = conce n t r a ti o n in the electrolyt e rang e d from "*< G "D<gE5. %bout )<,<< < tons of ore per day 'ere tre a t e d to produc e abou t 3<< tons of copp e r daily, or approxi m a t e l y $<,<< < tons of catho d e Cu annu ally. % simplified flo'sh e e t of the 7CC2 SX circuit is sho'n in ;igure $D -"..

(i5ur e -8 @ ;lo'sh e e t for 7chan g a Copper plant 1n late "#C*, the %nam a x Comp a n y comple t e d their [DD million plant at T'in 0utte s , %ri&ona, to tre a t "<,<< < tons of oxide copp er per day to produc e )<,<< < tons of copp er each year -").. ;eed to SX rang e d bet' e e n 3 )g CuE5, and the raffinat e cont ain e d less than <.<*g CuE5. Spent electrolyt e from electro'in nin g cont aining abou t 3*g CuE5 and "C*gE5 of total sulph a t e stripp e d the Cu from the load e d solven t, resulting in a feed electrolyt e to E! cont aining abou t )<g CuE5. The flo'sh e e t is sho' n in ;igure $#.

(i5ur e -9 @ %nam a x solve n t extr ac tio n flo'sh e e t

The solven t extr a c tion circuit 'as design e d for a throu g h p u t of C<<< gEm, at a feed p+ 3.3 3.* and cont ainin g 3.$ ).3g CuE5. ;our stag e s of extr a c tion and 3 sta g e s of stripping 'ere use d in 3 par allel circuits. The first ) extr a c tion stag e s 'ere a,u e o u s continuo u s , the = th being orga nic continu o u s . The solven t consist e d of "3 "=W 51X $*7 in a Chevro n diluen t cont ainin g "*W aro m a tics . The raffinat e cont ain e d <.=g CuE5. The stripping 'as acco m plis h e d 'ith spen t electrolyt e at C"<gE m flo', cont ainin g ")#g + 3 S< = E5 and 3*g CuE5 at 4E% ratio of "< to produc e an electrolyt e cont ainin g #".*g + 3 S< = E5 and *<g CuE5. The loading 'as maint ain e d to close to maxi m u m to minimi&e the loading of ;e 'hich 'ould carry over to the tankh o u s e in the strip. ;or exa m pl e , at #CW 51X cap acity, the strip solution cont ain e d <.<<) g ;eE5, comp a r e d to <.<"= g ;eE5 at $$W loading cap a city. Thus ther e 'as a = fold incre a s e in the ;e cont e n t , 'hich 'ould ther efor e re,uir e a = fold blee d in the tankho u s e . Treat m e n t of Conce n tr at e d Solutions % flo'sh e e t for the tre a t m e n t of conce n t r a t e d copp er solutions, arising from sulphuric acid dissolution of a chalcopyrit e conc e n t r a t e is sho'n in ;igure C< -C.. The leach solution cont ain e d , in gE5@ 3).3 Cu, "D.) 7i, ".3D Co, $.)= ;e at p+ ".3. ;ollo'ing pres s u r e leachin g, filtration and 'as hing, the filtrat e, at approxi m a t el y *< < C goes to solven t extr a c tion, to be cont a c t e d in thre e sta g e s of mixer settlers 'ith 3<W Felex "<< in Solves s o "*<, cont ainin g bet' e e n "< and 3<W of a modifier such as isodec a n ol or nonylph e n ol.

(i5ur e )$ Treat m e n t of Cu 7i Conce n tr a t e s by Press ur e 5each and Solven t Extraction The load e d solven t is stripp e d in 3 to ) sta g e s 'ith sulphuric acid to recov er the copp e r as an electrolyt e at abou t =<g CuE5 to feed to electrolysis. The stripp e d solve n t is 'ater 'as h e d and return e d to extr a c tion. The nickel cobalt raffinat e , cont ainin g also iron, is neutr ali&e d to precipita t e the iron, and the cobalt and nickel recov er e d sep a r a t el y by anot h e r solven t extr ac tio n proce s s , such as the us e of :3E+P% at p+ * -D,#.. (itric Acid Systems 1f the leaching condition s are not sev er e , and 'her e the acidity of the solution feed to the solven t extr a c tion circuit is in the rang e of p+ <.* to 3.<, then the proce s s describ e d for the sulph uric acid syst e m s 'ill apply. %lso, mixed acid leaching, using nitric and sulphuric acids, can result in a solution am e n a bl e to solven t extr a c tion proce s sin g. Copp er sulphid e conc e n t r a t e s hav e bee n leach e d in nitric acid by Fennec o t t -"<., and the studie s sho' e d that in tre a tin g a chalcop yrit e bornit e conce n t r a t e , #DW of the copp e r 'as solubili&ed. The copp e r 'as recov er e d from the leach solution s, an aly&ing, in gE5@ *< Cu, ) ;e, *C 74 ) , *3 S< = , using 51X $*7, and controlling the e,uilibriu m p+ during extr a c tion, 'ith lime. Stripping 'as acco m plis h e d using ".*2 + 3 S< = . The flo'sh e e t describing the Fenn eco t t proc e s s is sho'n in ;igure C".

(i5ur e )2 @ ;lo'sh e e t for proce s sin g Copp er conce n t r a t e 'ith nitric acid Chloride Systems 1n leach solution s cont ainin g small amo u n t s of chloride, e.g. "2, the usu al extr a c tion proc e s s e s can be practic e d as sho' n for the sulph a t e or nitrat e syst e m s . +o'ev er, in stron g chloride or hydroc hloric acid me di a, met als that form anionic chloride compl ex e s 'ill be extr ac t e d by such extr a c t a n t s as T0P or amin e s , as not e d in the section on Extract a n t s . 1nves tig a t o r s at the 7ation al 1nstitut e of 2etallurgy -712. in Sohan n e s b u r g hav e pilote d a proc e s s of ferric chloride leachin g of sulphid e conce n t r a t e s follo'e d by recov e r y of copp er by solven t extr ac tio n and electro'inning -"".. Copp er 'as recov er e d from the leach li,uors 'ith 51X $=7, the load e d solve n t 'as scrub b e d to reduc e the iron and chloride levels, and the copp e r recov e r e d by stripping 'ith spe n t electrolyt e from the electro'inning plant. The flo'sh e e t is sho'n in ;igure C3.

(i5ur e .2 @ 712 ;erric Chloride leachin g circuit 2inem e t 8ech erc h e hav e describ e d a proc e s s to recov e r copp e r from sulphid e ores and conce n t r a t e s , combining cupric chloride leaching, solven t extr a c tion and electro'in nin g -"3.. The proce s s compris e s the follo'ing proc e s s step s @ -a. at m o s p h e ric leachin g at a p+ not gre a t e r tha n " and not gre a t e r than $<< m6, using cupro u s chloride, 'ith the forma tio n of cupro u s chloride, ferrous chloride and ele m e n t a l sulphur/ -b. sep a r a tio n of the leach solution into t'o stre a m s , in the one, air is in(ect e d to precipit a t e the iron as goet hit e 'hile at the sa m e time reg e n e r a ti n g leaching age n t for recycle. 1n the other stre a m cont aining, for exa m pl e , in gE5, *< Cu H , 3< Cu 3H , 3* ;e 3H , 3<< 7aCl, copp e r is extr a c t e d in the cupric stat e using )<W 51X $*7 in Escaid "<<, 'hile the ferrou s iron is not extr a c t e d . The one stag e extr a c tion is at p+ ", a te m p e r a t u r e of *< < C, and a mixing time of "< "* minut e s . %ir is in(ect e d during extr ac tio n to oxidi&e cupro u s to cupric and to improv e the kinetics. The oxidi&ing extr ac tio n proce s s also acco m plis h e s neutr ali&a tio n of the acid produc e d res ulting from the copp e r extr ac tio n, ther e b y maint aining full loading cap a city 'ith a minimu m num b e r of extr a c tion sta g e s . %lso, the leach a n t is reg e n e r a t e d in the proc e s s . %ny chloride ions on the solve n t are remov e d by 3 stag e s of scrub bin g 'ith 'ater or copp e r sulph a t e solution. Copp er is the n recov e r e d by 3 stag e s of stripping 'ith spen t electrolyt e and cath o d e copp e r prod uc e d by the conv e n tio n al electro'in nin g of copp e r sulph a t e solution. The stripp e d solven t is finally 'ater scrub b e d in one sta g e to remov e any

entr ain e d sulph a t e that 'ould oth er'is e be retur n e d to the extr ac tio n stag e . The ma(or portion of the raffinat e from the copp er extr a c tion is recycle d to the leaching stag e , 'hile a blee d stre a m is tre a t e d by solve n t extr a c tion or ion exch a n g e to recov e r any cont ain e d me t al value s. The flo'sh e e t for the 2inem e t proc e s s is sho'n in ;igure C).

(i5ur e )3 3 @ 2inem e t proc e s s for Copp er extr a c tion from chloride solution Al%aline Ammonium Sulphate Systems 4ne of the proble m s 'ith extr a c tion from an am m o ni a c al solution is that som e am m o ni a is retain e d -or extr ac t e d . in the orga nic pha s e . Cont ac t of this load e d solven t cont aining the am m o ni a 'ith spe n t electrolyt e can result in the forma tio n of am m o ni u m sulph a t e in the electrolyt e feed to electro'inning. !ith cons t a n t recycle of the spen t electrolyt e to stripping, the am m o ni u m sulph a t e 'ould build up and if not bled off, cryst alli&ation of the salt could occur in the tankho u s e . 0leeding such a stre a m is not econ o mic, and in fact is not nec e s s a r y, bec a u s e the am m o ni a in the load e d solven t is rea dily reduc e d in conce n t r a ti o n by 'ater 'ashin g the solven t prior to stripping 'ith the spen t electrolyt e . 2ost not a bl e perh a p s of the alkaline appro a c h , is the %nacon d a %rbiter proce s s , 'hich is ess e n ti ally a modification of the Sherritt >ordon

Proces s , and making use of solven t extr a c tion. %t %nacon d a , 2onta n a , 'her e %nacon d a alre a d y had a conv e n tio n al smelt e r, a ne' plant incorpor a tin g their proce s s 'as comple t e d in "#C= 'ith a cap acity of )$,<< < tonsEye a r at a rate of "<< tons of copp er per day. The copp er conc e n t r a t e s are tre a t e d by lo' pres s u r e -oxyg e n partial pres s u r e *psia., alkaline leaching 'ith am m o ni a and oxyg e n , tog e t h e r 'ith special agita tion techni, u e s . Copp er that is solubili&ed is extr ac t e d from the clarified solution using 51X $*7, follo'ed by stripping 'ith spe n t tankho u s e electrolyt e to recov er the copp er. The flo'sh e e t of the proce s s is sho' n in ;igure C= -")..

(i5ur e )* * @ Simplified flo'sh e e t of the %rbiter proc e s s 1n the alkaline extr a c tion 'ith 51X $=7, extr a c tion kinetics are rapid, 'ith #*W e,uilibriu m being att ain e d in * seco n d s -"=., and ther efor e stag e re,uir e m e n t s are minim al. %lthoug h the kinetics are fast, >en er al 2ills -"*. reco m m e n d the us e of mixer settler s, 'ith 3 minut e mixer rete n tio n time s , and settlers design e d at 3 galEminEft 3 of total flo'. ;igure C* sho's the sch e m a ti c flo'sh e e t for am m o ni a leaching of copp e r scra p follo'ed by solve n t extr a c tion and electro'in ning -"=..

(i5ur e .) @ Copp er scrap %mmonia leach SXGE! circuit % som e ' h a t similar proce s s has bee n dev elo p e d by Pears o n -"*. for the recov er y of copp e r from bearin g me t al scra p. %mmonia c al am m o ni u m carbo n a t e solution, tog e t h e r 'ith air, are us ed to selectiv ely leach the copp e r. 51X $=7 extr a c t s the copp er, 'hich is stripp e d 'ith spen t electrolyt e from electro'in nin g. The extr a c tion raffinat e is retur n e d to the dissolution reac tor. The flo'sh e e t is sho'n in ;igure C$.

(i5ur e )) @ Copp er scrap %mmonia leach SXGE! circuit % proce s s using 51X $) for the extr a c tion of copp e r from am m o ni a c al solution, in the pres e n c e of cobalt and nickel, has be e n describ e d by 8itcey and 5ucas -"$.. The effect of alkalinity and -7+ = . 3 S< = conce n t r a ti o n are sho' n in ;igure CC. E,uilibriu m isoth e r m s for the extr a c tion of copp er 'ith 51X $) from a solution at p+ D.<, cont ainin g =*.Dg 7iE5, "".3g CuE5, <.D3g CoE5, and 3C3g -7+ = . 3 S4 = E5, are sho'n in ;igure CD. 1n ;igure C# is sho'n a diagr a m m a t i c flo'sh e e t of the propos e d proce s s for the

extr a c tion and sep a r a tio n of copp er from nickel and cobalt, pres e n t toge t h e r in an alkaline am m o ni u m sulph a t e leach solution. The solve n t is purified by scrub bin g 'ith a copp e r am mi n e solution cont ainin g )<<g -7+ = . 3 S4 = E5 at p+ D.

(i5ur e .. @ Effect of -7+ = . 3 S4 = conc e n t r a tio n and p+ on Copper extr a c tion

(i5ur e .8 @ E,uilibriu m isoth e r m s for 51X $) G Copper

(i5ur e .9 @ Propos e d flo'sh e e t for the tre a t m e n t of 7i Cu ore by an am m o ni a SX proc e s s Subs e , u e n t 'ork -"C. on similar alkaline leach solution s 'as report e d for the extr ac tio n and sep a r a tio n of copp e r from such me t al s as nickel, cobalt, and &inc that could occur in the alkaline leaching of sulphid e conc e n t r a t e s . The extr ac t a n t 'as <.*2 Felex "<< in Solves s o "*<, and cont ainin g "< vEo isodec a n ol as modifier. 1n a syst e m cont ainin g e,u al ,ua n titie s of copp e r, nickel, and cobalt, an incre a s e in -7+ = . 3 S< = conc e n t r a ti o n from *< to *<<gE5, toge t h e r 'ith an incre a s e in e,uilibriu m p+ from C to # res ult e d in a decr e a s e in extr ac tio n of copp e r, incre a s e in cobalt extr a c tion, 'hile nickel loading rem ai n e d relativ ely const a n t and lo', at O <." gE5. E,uilibriu m isoth er m s for Cu, Un, and Co are sho'n in ;igure D<, and in ;igure D" is sho'n the effect of -7+ = . 3 S< = conce n t r a ti o n and e,uilibriu m p+ on the extr ac tio n of copp e r, from a Cu 7i Co -7+ = . 3 S4 = syst e m . ;rom a feed solution cont aining *gE5 each of copp e r and &inc, the results in ;igure D3 sho' that both an incre a s e in the -7+ = . 3 S< = conce n t r a ti o n and e,uilibriu m p+ improv e d the ratio of CuEUn in the load e d solven t from * to D<. The tot al met al loading 'as approxi m a t el y "$gE5. Comp a r a bl e extr a c tion results using -7+ = . 3 C< ) sho' e d that althou g h this syst e m can be use d, the discrimin a tio n of copp e r over &inc is slightly less tha n 'ith the -7+ = . 3 S< = syst e m . %lso 'ith incre a sin g -7+ = . 3 C< )

conc e n t r a ti o n and p+, the discrimin a tio n of copp e r over &inc is incre a s e d only at the lo'er -7+ = . 3 C< ) conce n t r a ti o n. The selectivity of &inc over nickel 'as high er in the sulph a t e syst e m tha n in the carbo n a t e syst e m , over the p+ rang e and salt conc e n t r a ti o n s inves tig a t e d . The UnE7i ratio gen e r ally improv e d 'ith incre a sin g salt conce n t r a tio n sho' n in ;igure D) for the -7+ = . 3 S< = syst e m .

(i5ur e 80 E,uilibriu m extr ac tio n of Cu, Co 9 Un from alkaline solTn 'ith Felex "<<

(i5ur e 8$6 Extract a bility of Copp er 'ith Felex "<<

(i5ur e 82 @ Effect of e,uilibriu m p+ and -7+ = . 3 S< = conc e n t r a tio n on the sep a r a tio n of Cu 9 Un 'ith Felex "<<

(i5ur e )- @ Effect of e,uilibriu m p+ and -7+ = . 3 S< = conc e n t r a tio n on the sep a r a tio n of 7i 9 Un 'ith Felex "<< % proce s s for the recov er y of Cu from am m o ni a c al etch li,uors -ll*g CuE5, ")*g 7+ ) E5 and "*<g Cl E5., 'as dev elop e d -3<. using a mixe d extr a c t a n t

syst e m . This consist e d of =<W 6ersatic "< H "<W %corga P*"<< in Shell "=< diluen t. The flo'sh e e t for this syner gis tic mixtur e is sho'n in ;igure D=. The mixtur e res ult e d in incre a s e d rate of extr ac tio n and a lo' "g CuE5 raffinat e for recycle to leachin g. Conve n tio n al proc e s s e s reduc e the feed conc e n t r a ti o n to only abou t "<<g CuE5 for recycle. The Cu is scrub b e d to recov er the am m o ni a and the n stripp e d 'ith + 3 S< = . Electro'innin g of a carbo n tre a t e d strip li,uor produc e d smoo t h, comp a c t depo sits.

(i5ur e ). @ Sche m a tic for tre a tin g etch solution for Copp er recov e r y 4ne of the early extr a c t a n t s by Shell, S2E *3#, exhibite d excellen t extr a c tion char a c t e ris tics for Cu, Un, Co 3H and 7i from am m o ni a c al solution -3l.. This reag e n t 'as subs e , u e n t l y boug h t from Shell and no' mark e t e d by Cognis -+enkel. as 51X D=. % typical extr ac tio n isoth er m for the extr ac tio n of Cu from am m o ni a c al solution, and comp a r e d 'ith 51X *=, is given in ;igure D* -"#.. This reag e n t is no' in use in am m o ni a c al circuits in %ustralia for the sep a r a tio n and recov e r y of 7i from Co.

(i5ur e )8 ) @ Copper extr ac tio n isoth e r m s from am m o ni a "odern O0erations Since thos e early Cu SX E! plants , ther e hav e be e n plants broug h t into oper a tio n. 7o', abou t "* 3#W of copp e r produc tio n is derive d from SX E!. 0y "##$, plant at El %bra in Chile 'as com mis sio n e d to produc e catho d e grad e % copp e r -8ead e t t e 9 To'ns on.. nu m e r o u s similar the 'orld primar y the large s t single 33*,< < < t p a of 52E

0y early "##D ther e 'ere abou t *< oper a tin g plants , 'ith a total ann u al produc tion of gre a t e r tha n one million tonn e s . Chile is still the large s t produc e r, as sho'n in ;igure D$ -33.. The selectivity, as in mos t SX oper a tio n s , 'ill be enh a n c e d if maxi m u m loading is att ain e d , so as to \s,ue e & e offT impurities such as iron. %lso, the loading and ther efor e the sta g e re,uir e m e n t s can be affect e d by solve n t conc e n t r a ti o n -;igure DC.. 0y incre a sin g the p+ of extr a c tion, ther e is an incre a s e in loading and ther efor e ag ain a decr e a s e in the num b e r of stag e s re,uire d -;igure DD.. 4PE8%T17> 5E%C+ SX E! P5%7TS "##C CHILE ? 20 0 2 @
:16. 8. T421C, C4:E5C4 E5 %08% :16. C+?B?1C%2%T% ESC47:1:% U%5:16%8 CE884 C4548%:4 E5 TES484 B?E08%:% 05%7C% 542%S 0%A%S C455%+?%S1

&LA"T CA&ACITY ?1T Cu B: e ar @

3D< 33* "D< "3* "3* ")< C* C* $< *<

21C+155% 2%7T4S 05%7C4S 2%7T4 6E8:E :16.S%56%:48,C4:E5C4 %7:%C4554 C408E C%5ET% E5 C408E E7%21 16%7 U%8 B?E08%:% TE71E7TE E5 S45:%:4 014C408E :16.TE71E7TE, C4:E5C4 54S 0847CES :4S %21>4S 4T+E8S

*< =* =* )3 3< "3 "< "< "< C $ $ $ * $=

Total C<ile
-8ef. @ Comp e n di o de la 2iner]a Chilen a, 3<<3 .

$- ) 0

USA %rimetco Aerringto n 7ev. %rimetco Sohnson Camp %ri&. %sarco 8ay %ri&. Cyprus 0agd a d %ri&. Cyprus Tohono %ri&. Cyprus 2iami %ri&. Cyprus Sierrita %ri&. 0+P Pinto 6alley 0+P 2iami 0+P San 2anu el Phelps :odg e 0urro Chief Tyron e 72 Phelps :odg e Chine 72 Phelps :odg e 2orenci %ri&. Total USA A(RICA UCC2 Chingola Uambi a 2unya ti Uimb a b ' e Total A!ri9 a AUSTRALIA 0+%S S% >irilamb o n e 7S! >unpo' d e r Bld. 4lympic :am S% = "D # D <<< <<< <<< <<< "<< <<< D <<< $0 8 00 0 * = =< ") "3 $3 3# D "3 3* C" $" 3D= D=< <<< <<< =<< =<< <<< <<< D<< *<< D<< *<< <<< =<<

-3 0 -* 0

7ifty !% Cloncurry Bld. 2urchison Total Aus tr a li a ME'ICO Cana n e a " Cana n e a 3 2exican a :e Cobre Total Me8i9 o

"$ *<< * <<< * *<< -- 00 0

"3 <<< )< <<< 3< #<< -2 90 0

&ERU 2inero Peru Cerro 6erde South e r n Peru Copp er Total &er u IRA" Sar Ches h m e h Total Iran CY&RUS +ellenic 2ining Total C:>ru s CA"A%A >ibralta Total Can a ; a +RA"% TOTAL $ <<< - 00 0 2 03 . )* 0 D <<< 8 00 0 "3 <<< $2 00 0 )) <<< 3< <<< )3 00 0

(i5ur e 8- @ 4pera tin g 5each SX E! Plants, "##C

(i5ur e 8. @ Effect of 8eag e n t Conce n t r a tio n

(i5ur e 886 Effect of p+

Re$erences ". +olme s , S., 4ptim a, 2arch "#C), pp. =C *". 3. Po'er, F.5., in Proce e din g s of 1ntern a tio n al Solven t Extraction Confer e n c e , 1SEC TC", The +agu e, Pub. Soc. Che m. 1nd., 5ondon, "#C", pp. "=<# "="*. ). 2c>arr, +.>., Eng. %nd 2ining Sournal, 4ct. "#C<, pp C# D". =. 2cCarr, +.S., Che m. Eng., %ug. "<, "#C<, pp. D3 D=. *. +olme s , S.%. and ;isher, S,;,C,, R:evelop m e n t of a Proce s s for Extraction of Copper from Tailings and 5o' >rad e 2aterials at the Chingola :ivision of 7chan g a Consolida t e d Copper 2ines Uambi aR pres e n t e d at the %dvanc e s in Extraction 2etallurgy and 8efining Symp o siu m, 1.2.2., 5ondon, "#C". $. >runig, S.F., RThe 8ole of Solven t Extraction in Extraction 2etallurgyR, pres e n t e d at Symp o siu m on Solvent 1on Excha n g e , %1ChE, Tucson, %ri&ona, 2ay, "#C). C. 8itcey, >.2., C122 0ulletin, $$, 7o. C)3, pp. C* D). D. 8itcey, >.2., and %shbrook, %.!., ?.S. Pate n t ),)# #,< * * , "#$D.

#. 8itcey, >.2., %shbrook, %.!. and 5ucas, 0.+., C12 0ulletin, San. "#C*. "<. Prater, S.:., Buen e a u , P.0., and +udso n, T.S., R% 7itric %cid 8out e to Proces sin g Copper Conce n tr a t e s R, pres e n t e d at the %nnual 2eeting, %12E, San ;rancisco. ;eb. "#C3. "". Paynt e r, S.C., Sour. South %frican 1.2.2., 7ov. "#C), PP. "*D "C<, 8ef. 3D in article. "3. :em a r t h e , S.2., >ando n, 5., and >eorg e u x , %., Extractiv e 2etallurgy of Copper +ydro m e t a llurg y and Electro'innin g, 6ol. 3, Proce e di n g s of 1ntern a tio n al Symp o siu m "#C$, %12E, Pub. Port City Press, 0altimor e, ?.S.%., PP. D3* D=D. "). Fuhn, 2.C., %rbiter, 7., and Fling, +., C122 0ulletin, ;eb. "#C=, pp. $3 C#. "=. 2erigold, C.8., %gers, :.!., and +ous e, S.E., Proce e di n g s of 1ntern a tio n al Solven t Extraction Confer e n c e , 1SEC ^C", The +agu e, Pub. Sec. Che m, 1nd., 5ondon, "#C", pp. ")*" ")**. "*. Pears o n, :., 8ecla m a ti o n 1ndus trie s 8evie', Suly "#C3, pp. "< "". "$. 8itcey, >.2., and 5ucas, 0.+., Trans. C122, 6ol. 5XX6, pp. D3 D$, "#C3, also ?.S. Pate n t ),C$", 3=# -"#C).. "C. 8itcey, >.2., and 5ucas, 0.+., C12 0ulletin, ;eb. "#C*. "D. +iskey, 0. and 2uir, :., in SX Cours e not e s pres e n t e d in 2elbourn e ?niversity and 2urdoch ?niversity, 4ct 7ov. "##=, by >.2. 8itcey, >.!. Stev e n s , :. 2uir, and 0. +iskey. "#. 8itcey, >.2. and %shbrook, %.!., Solven t Extraction Principles and %pplications to Proces s 2etallurgy Part 1, Elsevier, 7e' Aork -"#D=.. 3<. 8itcey, >.2., and !ong, E.!., Proces s for 8ecov er y of Copp er from %mmo ni ac al Etch 5i,uors ?sing a 2ixed Extract a n t , Pres e n t e d at 1SEC^#), :env er/ and in Proce e din g s of 1SEC^#). 3". 8ice, 7.2., 7edve d, 2., 8itcey, >.2., The Extraction of 7ickel from %mmo ni ac al me di a and its Sep ar a tio n from Copper, Cobalt and Uinc ?sing +ydroxyoxi m e Extract a n t s . S. +ydro m e t a llurg y ), 7o. ", San. "#CD, pp. )* *=. 22. R!a5!tt/ (./ a.5 6+7.s+./ './ &ra%t$%a- As,!%ts +# 8+,,!r S+-9!.t E1tra%t$+.#r+ A%$5$% L!a%0 L$:u+rs/ &r!s!.t!5 at AL6A 1997 8+,,!r H;5r+ !ta--ur<;=+ru / O%t. 20-21/ 1997/ &!rt0 Austra-$a.

SECTIO" ,II
PRO- E"S ENCO!NTERED IN COPPER SO %ENT EXTRACTION P ANTS :r. >ordon 2. 8itcey >.2. 8itcey 9 %ssociat e s 1nc. C%7%:% Paper Pres e n t a t e d at the 1X 1ntern a tio n al 2eeting on Extractiv e 2etallurgy ?niversity of Sonor a, +ermo sillo, Sonor a, 2exico A/STRACT The first com m e r ci al solven t extr a c tion plant for the recov e r y of copp er beg a n produc tion in "#$#, or abou t )< years ago. :uring that period, various oper a tin g proble m s hav e bee n exp e ri e n c e d . 2any proble m s still occur, and re m ai n similar to the proble m s enco u n t e r e d in the early Cu plants . 1t is surprising that after such a lengt h y period of accu m ul a t e d exp erie n c e , and inde e d the previou s 3< years of the uraniu m exp e ri e n c e , 'hich similar proble m s are still encou n t e r e d . +o'ev er, in that time the cont a c tin g e,uip m e n t in Cu plant s has bee n similar, and met h o d s of oper a tin g the e,uip m e n t hav e not chan g e d significantly. Proba bly the large s t nu mb e r of solven t extr ac tio n plant s has be e n for the recov er y of copp e r. 0y no' thos e solven t extr a c tion oper a tio n s should be reas o n a bl y trouble free, for the proce s s is -or should be. design e d bas e d on@ soun d che mis tr y, met allurg y, engin e e rin g, and the prop e r oper a tio n al protocol. 0ase d on the proble m s exp erie n c e d by mos t oper a tio n s , it can prob a bly be said that the abov e fund a m e n t a l criteria for design are, to a larg e ext e n t, ignor e d. >ood che mis tr y and me t allurg y hav e define d a proc e s s / the bes t e,uip m e n t to achiev e mas s transf er mus t be select e d , and the cont a c t o r s oper a t e d prop e rly. 4ther'is e, proble m s occur in the solven t extr a c tion oper a tio n s . Thes e Rproble m s R are often not und e r s t o o d , for the plant oper a t o r s recog ni&e that som e t hin g is not perfor min g to design and so the Rsymp t o m R is tre a t e d and not the caus e . The proble m s or Rsymp t o m s R not e d by the oper a t o r s includ e the follo'ing@ lo' solven t loading poor ,uality produc t -loading to sat, scrub, selectiv e scrub, 'rong extr a c t a n t , co extr ac tio n vs selective extr ac tio n degr a d a tio n of solve n t -in proce s s and in Cu tankh o u s e . cruds and emulsions precipita t e s exce s siv e solids in the feed -reduc tio n to less tha n 3<pp m .

4f cours e the abov e has bee n the caus e of high oper a tin g costs in the sev er al plants bec a u s e the sourc e of the proble m has not be e n det er mi n e d , nor correc tiv e actions take n. 1nste a d , very exp e n siv e ancillary proc e s s e s andEor e,uip m e n t are often employe d to Rreduc e the impac t on the proc e s s econo mic sR This discus sion 'ill cite sever al plant situa tio n s encou n t e r e d by the aut h or, using exa m pl e s of Cu plant s to de m o n s t r a t e the various proble m s and the step s to improv e the oper a tio n. I"TRO%UCTIO" Solven t extr ac tio n as one of sever al unit oper a tio n s in hydro m e t a llurg y proc e s sin g and refining has no' bee n oper a tiv e for over =* year s. The dev elo p m e n t start e d 'ith the nucle ar indus try, first 'ith the refining of uraniu m using eth e r as the extr ac t a n t in the late "#=<^ s , soon follo'ed by T0P as the safer extr a c t a n t . Then the extr a c tion proce s s 'as take n to the uraniu m mills in the mid "#*<^ s to provid e an up grad e d uraniu m produc t. Plants and refinerie s to that dat e 'ere not large. Then 'ith the copp e r indus try recog ni&ing the pot e n ti al ben efits of the solven t extr ac tio n proce s s , the first large copp e r SX plant 'ent on stre a m in "#$#. Thus from that time the SX proce s s bec a m e gen e r ally acce p t e d and larger copp e r plants 'ere to be place d in oper a tio n. Since that time ther e hav e bee n a consid er a bl e num b e r of SX oper a tio n s , of all si&es in the miningE m e t a llurgic al indus try from the very small preciou s me t al s circuits and the radion uclide and reproc e s si n g circuits, the me diu m si&e rare and less com m o n bas e met als , and to the larger bas e met al plants . 7o' ther e are proc e s s e s dev elo p e d for virtually every met al in the periodic table of ele m e n t s . Som e of the proce s s e s are in oper a tio n, som e hav e reac h e d the pilot plant stag e , 'hile other s are still in the dev elop m e n t and optimis a tio n stag e s . There are ma n y asp e c t s to be consid e r e d in of the solve n t extr a c tion proce s s , and includ e the follo'ing import a n t are a s @ Che mis tr y Extract a n t s , 2odifiers, :iluent s 2ass transf er :isper sion and Coales c e n c e E,uip m e n t Selection and 4per a tio n Econo mics Environ m e n t a l and Solvent 5osse s

%ll impac t on the possibility of the succ e s sful design, and if som e are partially ignor e d then proble m s in the plant oper a tio n can be anticip a t e d .

1n this pap e r, sev er al copp e r plant s exp erie n cin g proble m s in the oper a tio n 'ere exa mi n e d and solution s 'ere propo s e d and imple m e n t e d to incre a s e the over all efficiency and ther e b y reduc e the oper a tin g costs. Specific deficiencie s are not e d , and also are a s 'her e modification s could res ult in subs t a n ti al improv e m e n t s in plant oper a tio n s . The RkeyR in all situ a tion s 'as to first det er mi n e , logically, the possible caus e of the Rproble mR by@ char a c t e ri&ing the Rproble mR by various analys e s verifying Rsusp e c t e d caus eR in benc h test s subs e , u e n t testin g on a continu o u s circuit det er mi nin g, by test s, possible solutions to the proble m testin g options in a continu o u s circuit evalu a tio n of the relativ e econo mics of the tre a t m e n t proce d u r e s selection of the bes t option and application to the plant

&LA"T &RO/LEMS A"% ASSES SME"T The plants that are cited 'ere ass e s s e d as reg ar d s plant perfor m a n c e , sa m pl e s 'ere take n and analys e d , cruds 'ere char a c t e ri& e d -8itcey, >.2., "#DD., and reco m m e n d a t i o n s ma d e to improv e the total perfor m a n c e and thus reduc e costs.

+i ralt ar Co>> e r Min e s The >ibraltar 2ines in 0ritish Columbi a, Cana d a , beg a n oper a tio n of their he a p leach solven t extr ac tio n electro'in nin g circuit in late "#D$. The solven t syst e m 'as *W %corga *<*< in Shell "$< diluent. The plant 'as by 0echt el, consistin g of = extr ac tio n and " strip stag e to tre a t a feed solution cont ainin g <.D g CuE5. Prior to electro'in nin g the strip is pas s e d throu g h a carbo n to' er to remov e any orga nic. 1t 'as not long after start up befor e serious crud dev elo p e d , particularly in the stripping circuit. The proble m 'as attribu t e d to eith er, or both, the degr a d a tio n of the extr ac t a n t and diluen t. They 'ere una bl e to run orga nic continuo u s due to incre a s e d emulsion proble m s , so the oper a tio n 'as a,u e o u s continuo u s . The solven t and the crud 'ere first exa mi n e d . The solven t 'as very black in colour./ the crud 'as a thick, bro'n almo s t comp a c t ma t e ri al,

sitting at the interfac e . 1n addition, ther e 'as a grey mat e ri al on the botto m of the crud solution, having the consist e n c y of ore slimes . Comp a ris o n of fresh diluen t s , 'ithou t any %corga rea g e n t pres e n t , result e d in a crud 'hen cont a c t e d 'ith the preg n a n t feed, so the real proble m 'as not of degr a d a ti o n of the extr ac t a n t or diluent. Tests indicat e d that the plant solve n t cont ain e d som e t hi n g that 'as succe s sf ully remo v e d by a 'as h 'ith <." 7 7a4+ solution, as the tre a t e d solven t 'as retur n e d to its nor m al stra' colour. +o'ev e r, on subs e , u e n t cont a c t 'ith fres h preg n a n t feed, a stringy crud res ult e d , indicatin g the proble m 'as due to the feed solution. 1nfrare d analys e s 'ere perfor m e d on the original plant solven t and comp a r e d to a lab stripp e d solve n t -plant solve n t that had bee n sub(ect e d to acid stripping, caus tic 'as h, extr a c tion and stripping.. 7o carbox ylic acids 'ere det e c t e d , but the tre a t m e n t remov e d som e peaks , 'hich could be degr a d a ti o n produc t s of the ma n uf a c t u r e or other orga nic additive s that are add e d in leaching and electro'inning. Chara c t e ri& a tion studie s of the crud 'ere ma d e by X8;@ Slimes -very fine, grey and difficult to filter. Si ma(or/ also %l,Ca Crud -bro' n, porridg e like consist e n c y of larg e flocs./ Si ma(or but one tent h the conc e n t r a tio n of slimes The slime s are due to the fine ore articles getting throu g h the extr a c tion circuit into stripping. Bualitativ e crud bre aking tes ts indicat e d a high amo u n t of solven t pres e n t / and that Si and pres e n t exist e d as colloids.

8eco m m e n d a t i o n s and Conclusions @ 4re fines are pres e n t and no clarification is pres e n t prior to solven t extr a c tion, and no scrub stag e is employe d 'hich may hav e overco m e the proble m. Clarification and a scrub sta g e should be installed. 0eca u s e ther e is the tend e n c y to' ard s emulsion forma tio n, eve n in the pres e n c e of keros e n e only, this sugg e s t s that the syst e m is una bl e to tolera t e high she a r. Even thoug h the plant continu ally reduc e d the si&e of the impeller in an att e m p t to run succe s sf ully, the modifications 'ere not succ e s sful. % re design of the pum p mix 'ould be re,uire d, or the application of a differe n t type of cont a c t o r device. The test s indicat e d no proble m 'ith the diluent and degr a d a tio n, but the caus tic 'as h did remov e orga nic cons titu e n t s from the solven t, possibly degr a d a tio n prod uc t s of the %corga andEor the leaching and

electro'inning circuit additive s. 8eco m m e n d e d that a continu al blee d of the stripp e d solve n t be tre a t e d 'ith caus tic to maint ai n its integrity by removin g the non stripp a bl e mat e ri al. The orga nic additive s add e d in the electro'in nin g circuit should be exa mi n e d as to the possible caus e of the proble m . Mt Isa Min e s Li7it e ; The solven t extr a c tion plant of 212 'as locat e d at the smelt e r at 2t 1sa, centr al Buee n sl a n d , %ustralia, and 'as com mis sio n e d in "##< to produc e "< tEd catho d e copp e r. The solve n t extr a c tion electro'inning is no' shut d o' n . 1t 'as a he a p leachin g oper a tio n for recov er y of oxidi&ed copp e r. The P5S cont ain e d ".* ".# gE5 Cu, and by eva p or a tio n, conce n t r a t e d to ).* gE5 Cu. %s in ma n y similar typ e s of hea p leaching oper a tio n s , clay and fines in the circuit follo'ing a heav y rain 'as com m o n . There 'ere 3 stag e s of extr a c tion, 'ith )W 51X #D= and a single stag e of stripping, but no scrub sta g e . The mixer settler s 'ere Frebs design. 4rga nic continuo u s 'as run if possible to minimi&e crud. Entrain e d solven t in the strip solution 'as remo v e d by a Samison cell prior to electro'inning Proble m s exce s siv e cruds 'ere produc e d , particularly follo'ing a period of rain, 'hen consid e r a bl e clays 'ere pres e n t in the feed the cruds 'ere comp o s e d ess e n ti ally of clays, and the solven t 'as only rele a s e d slo'ly by sitting or by agita tio n 'ith diluent high entr ain m e n t loss e s decr e a s e in extr a c tion efficiency, and plant sus p e c t degr a d a ti o n of rea g e n t

8eco m m e n d a t i o n s %nalys e s and char a c t e ri& a tion of crud 1nstallation of a scrub stag e 1nves tig a t e possible use of a differe n t typ e of cont a c t o r :eter mi n e 'het h e r the solven t is being degr a d e d or is fouled Met al s --/HAS ?/roC e n Hill As s o 9 i a t e ; S7 e l t e r s @

&a s 7 i n 9 o Co>> e r

The 0+%S lead smelt e r is locat e d in the north e r n part of the stat e of South %ustralia, at Port Pirie, and is still in oper a tio n. The feed to leaching is a Cu Pb S mat t e , and leachin g is in sulph a t e chloride me diu m . The clarified leach solution cont ains abou t 3< =< gE5 Cu at p+ ".*. The copp e r solven t extr a c tion circuit consists of 3 stag e s of extr a c tion, " scrub and 3 strip sta g e s . The extr a c t a n t is nor m ally "< "*W %corga *$=<, altho u g h has varied up to )< W. They hav e bee n able to run a,u e o u s continu o u s throu g h o u t the circuit. Proble m s slo' pha s e disen g a g e m e n t and lo' throu g h p u t eve n thoug h periodic clay tre a t m e n t reduc e d perfor m a n c e of the solve n t, consid e r e d by the plant to be degr a d a tio n -particularly since ther e 'as an introd uc tio n of 2n into the feed to the plant. crud and emulsion s, and thus high solven t loss es build up of gyps u m in the settlers re,uir e s remov al every 3 ) mont h s high solve n t entr ain m e n t loss e s occa sion al high carry over of chloride into the tankho u s e

8eco m m e n d a t i o n s Evaluation of 'etting char a c t e ris tics of t'o dissimilar ma t e ri als for the picket fenc e in the settlers to enh a n c e pha s e sep a r a tio n and thus to incre a s e throu g h p u t Exa min a tio n of the solve n t for poisoning andEor degr a d a tio n Chara c t e ri& a tion and an alys e s of the crud, det er mi n e the caus e , and det e r mi n e met h o d s to prev e n t the form a tio n Exces siv e mixing time pres e n tly in mixers, and thus produc tion of fine droplet s ma y re,uir e baffling of the mixer outflo' to decr e a s e the linear velocity Possibly the succe s sf ul introd uc tio n of differe n t mat e ri als in the picket fence s The reduction of mixing time tog e t h e r 'ith running the extr ac tio n orga nic continuo u s might reduc e the gyps u m proble m. %ddition al extr a scrub sta g e for chloride remo v al may be re,uire d, as this is prob a bly (ust a situa tio n of e,uilibriu m in 'hich

insufficient stag e s are available. %ltern a tiv ely, perh a p s a scrub 'ith 7a 3 S4 = could be mor e effective. Scrubbin g in a puls e column -ma n y sta g e s . ma y be re,uire d. "i!t: Co>> e r Min e The 7ifty oper a tio n is locat e d in the north 'est e r n part of !est er n %ustralia, and 'as originally o'ne d and oper a t e d by !est er n 2ining, and has rece n tly be e n sold. The plant 'as design e d and constru c t e d by !est er n 2ining. Production com m e n c e d in "##). The copp er oxide ore is leach e d to produc e a solution cont aining abou t C.D gE5 Cu, and abou t 3 gE5 ;e and <.* gE5 2n. The Frebs design e d circuit consists of 3 stag e s of extr a c tion, a 'as h stag e , and 3 strip stag e s . The solve n t is 3)W %corga *$=< in Shellsol 3<=$ diluent. There 'ere ma n y engin e e ri n g proble m s , such as@ Samison cell at 'rong heigh t and impos sible to oper a t e befor e repiping 5ines from electro'in ning cells too narro', and full throu g h p u t could not be achiev e d 5eaching 'as poor

The start up by the plant oper a t o r s called for abou t $<W of design cap acity. !hen the proble m s of poor pha s e disen g a g e m e n t dev elo p e d , the throu g h p u t 'as reduc e d to abou t *<W. The proble m still persis t e d , and in fact 'as beco min g 'ors e. So the throu g h p u t 'as furth e r reduc e d to =<W and finally )<W. This all occurr e d over abou t the first year of oper a tio n. 0y that time all sorts of Rproble m s R had bee n identified by the oper a t o r s and ma n a g e m e n t . Proble m s crud in each stag e , slo' settling and lo' throu g h p u t una ble to maint ain orga nic continu o u s in all stag e s solven t very black and a clay tre a t m e n t restor e s it to a 'orkable situa tion app a r e n t degr a d a ti o n of the solve n t, attribut e d to 2n pres e n c e in tankho u s e in spite of the fact that ther e is a scrub sta g e , 2n is pas sin g throu g h into the E! susp e c t e d loading of 2n in the reduc e d stat e and oxidi&ed in tankho u s e -not prov e n. to per m a n g a n a t e . bec a u s e of the reduc e d throu g h p u t , due to slo' pha s e disen g a g e m e n t , the ret e n tio n time in the mixers is abou t $ minut e s , allo'ing for eve n finer emulsions to be produc e d , as 'ell as to extr ac t impurities consid er a bl e turbul e n c e in the mixers

the Samison cell is only abou t *< C<W effectiv e

5abora t or y Tests test s 'ith plant solve n t, plant feed and fres h solve n t indicat e d that the plant solven t 'as badly fouled, and the sep a r a tio n time 'as at leas t 3.* time s long er. %ny possible small conce n t r a tio n of a cont a mi n a n t that might hav e bee n in the feed solution did not sho' an effect in such a test. tre a t m e n t of the solven t 'ith dilute 7a4+ 'ash, reduc e d the sep a r a tio n time in subs e , u e n t extr a c tion from "D< to =< secon d s . 'as hing 'ith 7a; solution also 'as e,u ally effective/ ho' ev e r analys e s of the yello' raffinat e 'ash sho' e d no inorg a nics, and orga nic constitu e n t s 'ere not analys e d . bre aking of the crud, 'hich relea s e d ma t e ri al similar to the ore slimes , 'as mos t effectiv e 'ith eith er an oxidi&ing peroxid e or a reducin g tre a t m e n t 'ith thios ulph a t e and ure a. analys e s of cruds indicat e d similar and high cons titu e n t s in extr a c tion, scrub and strip, 'ith the Si as high as =DW, toge t h e r 'ith ma(or %l, ;e, 2g, F, plus minor Cu, Ti, 7a, P, S.

8eco m m e n d a t i o n s %nalys e the orga nic and 'as h e s for possible poisons 6erify the possible caus e of the inefficiency, due to a combin a tio n of cruds, slo' settling, solven t poisoning 4ptimis e a solve n t tre a t m e n t proc e s s Establish 'het h e r solven t degr a d a tio n det er mi nin g active extr a c tion sites is actu ally occurring by

8un small mixer settler circuit to verify an improv e d circuit prior to plant application 1nves tig a t e possible chan g e in pres e n t scrub nec e s sit y of an addition al special scrub 1nves tig a t e running at clos er to design levels and the possible

%s a result of the inves tig a tio n, subs e , u e n t test s at the small pilot scale subs t a n ti a t e d that the ma(or proble m in the circuit 'as not

running to the design flo's. The long er the mixed pha s e s 'ere in cont a c t und er high she a r, the gre a t e r the crud, the 'ors e the emulsions , the slo'er the phas e sep a r a tio n rate s , and eve n t u al the nec e s sit y to shut do'n. %lthoug h the clay tre a t m e n t that 7ifty use d on the orga nic 'hen phas e sep a r a tio n rate s bec a m e slo' 'as reas o n a bl y succ e s sful for up to abou t 3 'eeks, the tre a t m e n t 'as ag ain nece s s a r y. The dilute caus tic tre a t m e n t of the solve n t app e a r e d to be consid er a bl y mor e effective for maint ai nin g solven t ,uality, and continu o u s tre a t m e n t of a blee d stre a m 'as reco m m e n d e d . +irila 7 o n e Co>> e r Min e This plant is locat e d in the stat e of 7e' South !ales in %ustralia. %fter som e initial proble m s follo'ing start up in "##), and the initial first year of prod uc tio n, the plant had very little proble m s , and prod uc e d excelle n t ,uality catho d e copp e r. The leach from the he a p s cont ains abou t ".$ ).$ gE5 Cu. The plant consist s of 3 extr ac tio n sta g e s , using "CW 51X #D=, and a single strip sta g e . There is no scrub sta g e . % Samison cell effectiv ely remo v e s entr ain e d solven t from the electrolyt e, 'hile a conve n tio n al flotation cell 'as ineffectiv e. The solven t is periodically clay tre a t e d to maint ain efficiency. Proble m s crud in both circuits, and in stripping, the crud is often 'hite in colour high %l and Si in P5S difficulty in maint ai nin g orga nic continu o u s 2n proble m in the tankho u s e and app a r e n t degr a d a tio n of solve n t solven t dark and viscous slo' pha s e disen g a g e m e n t s high solve n t loss e s degr a d a tio n of solve n t -in proce s s and in Cu tankh o u s e .

5abora t or y Tests 'as hing solven t 'ith *W caus tic result e d in good pha s e sep a r a tio n s in subs e , u e n t extr a c tion s

8eco m m e n d a t i o n s Crud an alys e s and char a c t e ri& a tion studie s

1nstallation of a scrub stag e 1dentify 'het h e r solven t is degr a d e d or poison e d Close the ends of settler s to decr e a s e solven t eva p or a tio n 0affling of the mixers and settler s 1ncorpor a tio n of a solve n t tre a t m e n t stag e bas e d on 'hat has to be remo v e d

Ol: 7 > i 9 %a7 Co>> e r %t the 4lympic :am oper a tio n, locat e d in the north e r n part of the stat e of South %ustralia, ther e is a solve n t extr ac tio n circuit for the recov er y of copp e r follo'ed by anot h e r solve n t extr ac tio n circuit for the recov er y of uraniu m. The leach solution resulting from leaching of flotation tailings cont ainin g 3.* gE5 Cu. The Cu circuit at 4lympic :am consist s of 3 parallel extr a c tion circuits of 3 stag e s each, follo'ed by a scrub stag e and a single strip stag e . The 'ater scrub effectiv ely reduc e s the chloride cont e n t in the solve n t so it is not carried over into the tankho u s e . The Samison cell is not as effective as it might be in the tre a t m e n t of the strip electrolyt e, 'ith the amo u n t of fines in the electrolyt e , altho u g h reducin g the solve n t loss e s from )<pp m to O "<pp m . The solven t is sub(ect e d to a periodic clay tre a t m e n t to reduc e fouling.

Proble m s leach feed cont ains abou t *<pp m solids -abou t * tonsE' e e k ., and the fines ma t e ri al n settler s of both Cu and ? circuits. Solids in Cu circuit cont ain he m a tit e , (arosit e and gyps u m . Crud in all extr a c tion stag e s . som e crud in scrub stag e mud d y crud in strip stag e , similar to the ore fines/ also, a grey, slimy crud. solven t loss e s at abou t "*<p p m , and solve n t dark in colour, but no evide n t proble m solven t fouling, 'ith result a n t high raffinat e s chlorine evolution in the E!

8eco m m e n d a t i o n s ES olution s Pre 'as h the feed solution 'ith keros e n e to float the fine mat e ri al

1nves tig a t e possibility of use of a puls e colum n in the scrub stag e to mor e effectiv ely remo v e the fines Surfac e che mis tr y studie s re,uire d Check 7) : 3 for all agita t or s Chara c t e ri& e all cruds, analys e s re,uir e d/ dev elopin g crud bre aking, and crud gen e r a tin g para m e t e r s , and finally crud prev e n tio n me a s u r e s . 1nves tig a t e possible fouling of the solven t by the surfact a n t s used in clarification/ are they being degr a d e d to orga nic acids_ 2eas ur e redox in syst e m , and if high is degr a d a ti o n occurring of the solven t

Establish 'het h e r the solven t is being chlorina t e d and subs e , u e n tl y sulpho n a t e d 1nves tig a t e periodic solve n t tre a t m e n t 'ith perh a p s 7a;

+un > o D ; e r Co> > e r This copp er oper a tio n is locat e d in the centr al Buee n sl a n d are a, a couple hours drive from 2t 1sa, and 'as com mis sio n e d in "##<. The feed solution has primarily be e n produc e d by hea p leachin g, producin g feed solution cont aining * gEl Cu and "D gE5 ;e at p+ ".*. The leach solution is stor e d in a pond, and the solids allo'e d to settle 'ithout clarification prior to sen din g to the solve n t extr a c tion circuit. The plant use s #.$W %corga *$=<, eve n thou g h DW 'ould be the re,uir e m e n t , if not for the fact that the solve n t loading has be e n decr e a si n g . %ddition al %corga is periodic ally add e d in order to maint ain extr ac tio n. The solve n t is black, usu ally indicating that som e t hin g is hap p e ni n g. The leach feed cont ain s "<<p p m solids, and thes e solids, as crud, are trans p o r t e d throu g h o u t the circuit. The crud is disch ar g e d to a special pond 'her e it can rem ain for sever al mon t h s before recycle to the plant. The circuit compris e s 3 extr a c tion, " scrub, and 3 strip stag e s . Proble m s

high raffinat e s consid er a bl e solids in the P5S 'hich report s in the settler s crud at interfac e and throu g h o u t the orga nic pha s e decr e a si n g efficiency and the app a r e n t solve n t degr a d a tio n cont a mi n a n t poisoning high entr ain m e n t loss e s high solve n t lost in the crud

or

4bserv a tio n s , Chara c t e ri& a tion and Tests the slimy bro'n crud in the extr a c tion stag e s is prob a bly ore slime s the app a r e n t lo' loading, or app a r e n t degr a d a ti o n theory 'as test e d by tre a tin g the plant solven t 'ith a " 3W solution of 7a 3 C4 ) . The tre a t e d solven t conc e n t r a ti o n, as det er mi n e d by the 1C1 met h o d , indicat e d the solve n t to cont ain "=.$W %corga, comp a r e d to the plant -untr e a t e d solve n t. of "<W. The loading 'as, res p e c tiv ely, C.D" and *.)= g CuE5. Tests thus indicat e d that degr a d a ti o n had not occurr e d , but poisonin g had, 'hich could be re mo v e d . the stag e efficiency is lo', 'ith only )<W in E" and $*W in E3. This 'ould indicat e addition al sta g e s are re,uire d, or mor e solve n t. The p+ of extr ac tio n is as lo' as p+ ".=. consid er a bl e Cu re m ai n s on the solven t after stripping, 'hich 'ould ther efor e affect the loading. 1s the poor extr a c tion efficiency really as a res ult of poor stripping efficiency_ flotation test s on the P5S 'ith Shellsol 3<=$ remov e d solids, and the orga nic pha s e 'as a pale yello'. Tests re,uire d to det er mi n e 'het h e r this is due to extr a c t e d orga nic acids or other cont a mi n a n t s that 'ould foul the solve n t. both the plant solven t and the P5S cont ain e d extr a c t a bl e subs t a n c e s that can affect the pha s e sep ar a tio n time. That is, cont a c t of the P5S 'ith diluen t extr a c t e d an orga nic constitu e n t 'hich 'as yello' coloure d in the solven t. the crud on the botto m of the first strip settler cont ain s abou t 3<W Si. This see m s to be an app a r e n t relea s e from the solven t during stripping, prob a bly due to satur a tio n.

8eco m m e n d a t i o n s 1nves tig a tio n re,uir e d on particle charg e s to improv e the rate and comple t e n e s s of settling prior to solve n t extr a c tion

:eter mi n e 'het h e r the solven t tre a t m e n t prior to us e

recycle from the pond

re,uir e s

:eter mi n e 'het h e r the solids can be re mo v e d by flotation 5abora t or y degr a d a tio n test s on the %corga are re,uire d over time :eter mi n e the poison that is on the solve n t, as 'ell as det e r mi n e the orga nic impurity in the P5S that is being load e d by the solven t. 4ptimis e the stripping and electrolyt e to electro'inning E,uilibriu m isoth er m s are re,uir e d on the plant solve n t/ solven t reclaim e d from the pond/ sod a ash tre a t e d pond solve n t/ sod a ash tre a t e d plant solven t/ and comp a r e d to fresh solve n t. :eter mi n e 'het h e r the nonylph e n ol in the extr a c t a n t is being degr a d e d and providing a surfact a n t to the syst e m , res ulting in the occasion al serious cruds throu g h o u t the proce s s . :eter mi n e 'hat is holding the Si on the extr a c t a n t and relea s e d in stripping. 1s the Si pres e n t bec a u s e of a polym e r, such as a degr a d a tio n of the nonylph e n ol in the %corga_

+E"ERAL COMME"TS A"% SUMMARY There hav e bee n similar proble m s in ma n y other copp e r and non copp e r oper a tio n s encou n t e r e d in Cana d a , 0ra&il, Chile, %ustralia. Thes e includ e@ poor ,uality produc t cruds -precipit a t e s . and emulsions

1n mos t cas e s the caus e s of the proble m s could be attribu t e d to a fe' or all of the follo'ing oper a tin g par a m e t e r s , som e of 'hich 'ere not being perfor m e d correctly, or oth er s that 'ere not consid er e d as an import a n t factor@ loading to satur a tio n scrub bin g to re mo v e entr ain m e n t of feed selectiv e scrub bin g extr a c t a n t choice and conc e n t r a ti o n modifier choice -or none at all. diluent selection

co extr ac tio n vs selective extr ac tio n, p+ control kinetics e,uip m e n t selection and oper a tio n

O8i; a t i o n &ro l e 7 s 4ne gen e r al com m e n t relev a n t to the leaching and subs e , u e n t solven t extr a c tion is that of the oxidation pot e n ti al of the feed solution to solve n t extr a c tion. %n overd o s e of the oxidan t that might be nec e s s a r y during leaching, or the produc tion of an highly oxidi&ed specie s during leachin g or electro'in nin g, and the high oper a tin g te m p e r a t u r e of the circuit hav e caus e d serious degr a d a tio n of the extr a c t a n t s being use d. Closer control in the leaching, toge t h e r 'ith bett e r te m p e r a t u r e control in the extr ac tio n plant solved the proble m. The proble m of oxidation can be a proble m in oth er extr a c tion circuits, due to the pres e n c e of a highly charg e d species . Typical of the me t al s that can be exp e c t e d to caus e oxidation degr a d a ti o n of the orga nic are Co) H , 6*H, Cr$ H , 2nC H . The higher the valency stat e , the higher the oper a tin g te m p e r a t u r e , the longer the cont a c t time, all lead to degr a d a tio n proble m s .

So 7 e &ro l e 7 s %u e to Sili9 a 1t 'as evide n t in ma n y exa m pl e s that Si, in its various forms, could provid e a proble m, and enh a n c e the possibility for the forma tio n of cruds. ;ollo'ing are som e conclusion s -8itcey 9 !ong, "#DD/ 8itcey, "#D3, "#D*, "#D$.. The pres e n c e of Si can caus e or enh a n c e the forma tio n of cruds and emulsions . 2ost cruds are comp o s e d of Si as the ma(or constitu e n t , toge t h e r 'ith ;e 2g Ca %l and the me t al being extr ac t e d . ?nless ther e is a scrub sta g e bet' e e n extr ac tio n and stripping, Si and oth er impurities ma y carry over and app e a r in the strip produc t. 4rga nic continu o u s oper a tio n app e a r s to minimi&e emulsion forma tio n in the pres e n c e of Si. The pres e n c e of hu mic acids toge t h e r 'ith Si enh a n c e s emulsions and cruds, as does high she a r.

Solutions cont aining colloidal silica, in the a,u e o u s continuo u s syst e m , are sev er ely ret ar d e d in pha s e sep a r a tio n rat e s and ten d to form stable emulsion s. 7oticed in amin e s , alkylpho s p h a t e s and oxime s syst e m s . Colloidal silica and lo' molecular 'eight amin e s result in slo'er phas e disen g a g e m e n t than high er molec ul ar 'eight amin e s . 2ost emulsion s are produc e d by a third phas e emulsifier consisting of a colloidal subs t a n c e -such as silica alu min a, hydros ols or clays, ferric or alu miniu m hydroxid e or colloidal phos p h a t e . . Each emulsion or crud has its o'n char a c t e ris tics and re,uir e labor a t o r y identification. 2ethod s of identification includ e microsco pic, X ray diffraction, infrare d and emission spectr o g r a p hic tech ni, u e s . T0P emulsion s are sta bili&ed by silicic acid. Temp e r a t u r e , acidity and nat ur e of the a,u e o u s phas e hav e consid er a bl e influenc e on the stability of the T0P emulsion in the pres e n c e of silicic acid. Possible met h o d s of prev e n tio n includ e@ chan g e s in p+/ addition of flocculating age n t s to remo v e the emulsifier/ addition of disper sio n age n t s to disper s e the emulsifying pha s e / chan g e plant practice to avoid form a tion of the surfac e active mat e ri als/ addition of fluoride or oth er comple x to solubilise the silica colloid.

Criteri a Us e ; in A o= e E8a 7 > l e s 1n the list of proble m s cited by the oper a t o r s , ma n y 'ere not e d as sho'n earlier, and mos t of 'hich are sho' n belo'. Thos e not consid er e d , and 'hich 'ere found to be import a n t asp e c t s in solving the proble m s , are cont a c t o r e,uip m e n t selection and oper a tio n/ solven t -extr a c t a n t , diluent, modifier. selection/ loading to satur a tio n/ scrub bin g -'as h, and purification./ and controlled stripping. lo' solven t loading poor ,uality produc t -loading to satur a tio n, scrub, selective scrub, 'rong extr a c t a n t , co extr ac tio n vs selectiv e extr ac tio n degr a d a tio n of solve n t -in proce s s and in Cu tankh o u s e . cruds and emulsions precipita t e s exce s siv e solids in the feed -reduc tio n to less tha n 3<pp m . choice of e,uip m e n t and its oper a tio n selection of extr a c t a n t , -modifier. and diluen t

The plant ass e s s m e n t s hav e indicat e d that ther e are num e r o u s caus e s of plant inefficiency. +o'ev er one of the com m o n caus e s that has bee n de m o n s t r a t e d is that of the solve n t being fouled res ulting in decr e a si n g rat e s of coales c e n c e , decr e a s e d loading, and ultima t ely reduc e d throu g h p u t . The high she a r of mos t of the cont a c t o r s -high she a r mixer settlers ., tog e t h e r 'ith colloids of Si, %l, and ore slime s and fines enh a n c e s the proble m s . 2ore att e n tio n has to be paid during the proce s s design, piloting and ultima t e plant scale up to ens ur e that such possible costly proble m s 'ill not occur. Each plant 'ill be site specific, and ther efor e a good interfac e bet' e e n the met allurgis ts involved in the proce s s design and the engin e e r s involved in the plant design is nec e s s a r y. RE(ERE"CES 8itcey, >.2., !ong, E.!./ "#DD. Proc. 1SEC^DD, 2osco'. 8itcey, >.2., "#D3. Proc. "= th 1nt. 2in. Proces sin g Conf., Toronto. 8itcey, >.2., "#D*. Sournal +ydro m e t a llur g y, 6ol. "*, pp ** $". 8itcey, >.2., "#D$. Can 2et. Buart e rly, 6ol 3*, 7o. ", pp )" =).

SECTION %II PROCESSIN. O# CO"P EX -ASE "ETA S! PHIDES

Introd7ction :uring the pas t 3* years or mor e ther e has be e n consid e r a bl e res e a r c h and reso urc e s spe n t by various orga ni&a tion s throu g h o u t the 'orld on the att e m p t to proc e s s compl ex, fine grain e d sulphid e s . Thes e ores, cont ainin g CuEPbEUn and other value s are particularly found in Cana d a , %ustralia, 7or'ay, Spain and oth er countries . 0eca u s e of their finely diss e mi n a t e d nat ur e they do not res po n d

succe s sf ully to differe n ti al flotation to produc e sep a r a t e conce n t r a t e s 'ithou t high loss e s of value s to tailings. Thes e loss e s can amo u n t to perh a p s )<W or mor e of the value s . :uring the pas t C years C%72ET has be e n conduc tin g one of its ma(or efforts on the dev elop m e n t of altern a tiv e tech n olog y to the conv e n tio n al sulph a t e syst e m s for the comple x sulphid e s . 0oth Rin hous eR res e a r c h as 'ell as ext er n al contr a c t res e a r c h 'as perfor m e d . %s a result of an exa min a tio n of the Rstat e of the artR and a revie' of the litera t u r e , chloride met allurg y 'as select e d for the in hous e res e a r c h . The ext er n al proc e s s e s involved pres s u r e sulphuric acid leaching in one proc e s s and a roas t leach SX rout e for the other proce s s . 0efore a choice of a proce s s rout e ther e are various consid er a tio n s that hav e to be consid er e d such as impurities, by prod uc t s , possible purification rout e s , environ m e n t a l cons tr ain t s , en er g y re,uir e m e n t s , corrosion and costs. The entire integr a t e d circuit mus t ther efor e be consid er e d 'ith resp e c t to the en er g y, econ o mic s and environ m e n t . The optimi&a tion 'ill dep e n d upon the miner alo g y and its und er s t a n d i n g and ho' the fines of grind affects the libera tion of the met al value s . 2any solution purification rout e s are possible and ther efor e each has to be carefully consid e r e d in the flo'sh e e t design. The over all ob(ective s 'ere to dev elo p tech n olog y to@ incre a s e me t al s recov e r y incre a s e possible by produc t recov er y minimi&e environ m e n t a l proble m s ass ocia t e d D'ith dispos al pyrite, sulphur dioxide, and other und e sir a bl e 'ast e s

of

The proce s s mus t also be econ o mic. Table "C sho's the miner alo g y of a 0runs'ick 2ining and Smelting -Can a d a . compl ex sulph a t e ore, and Table "D the bulk conce n t r a t e analys e s of that ore as 'ell as 2c%rthur 8iver -%ustr alia.. Ta l e $) @ 2ineralog y of 0runs'ick 2ining 4re and Conce n t r a t e Ore Sphal erit e Pyrite >alen a Chalcopyrit e Buart& "3 " ) " "" Con9 e n t r a te *).$ )=.D =.* ).*

Ta l e $- @ Che mic al %nalys e s of 0runs'ick 2ining and 2c%rthur 8iver Anal: s i s E Un Cu Pb ;e Cd S Si4 3 %gV Vo&Eton /run s D i 9 C Minin 5 Ore Con 9 e n t r a te D.* )<.< <.3C <.C= )."* #.=D )<.< "#.# <.<* )C.# )$.$ <.33 )."< C." M9Art< u r Ri=er Ore #.C <."D =.= #.< ").$ )<.< ".) Con9 e n t r a te 3C.< <.*< "".< "3.D 3#." "<.D ).*

Process O0tions The four proce s s options are describ e d @ sulph a tio n roas t leach -S85. proc e s s pres s u r e sulphuric acid -PS%. leach proce s s ferric chloride leach -;C5. proce s s dry 'ay chlorina tio n

Sulphate Processes ;igure D# sho's the S85 proc e s s dev elo p e d by the 8es e a r c h and Productivity Council of 7e' 0runs'ick. The leach solution is purified by SX E! or ce m e n t a ti o n 'ith Un dust for Cu recov e r y. 1ron is precipita t e d by oxidation 'ith 2n< 3 and addition of limes t o n e . Cem e n t a ti o n remov e s Co, 7i, Cd. The Un is recov e r e d by electro'inning. The leach residu e is leach e d in brine to recov e r y %g. ;igure #< sho's the PS% proce s s dev elop e d by Sherritt >ordon res e a r c h . Purification of the leach solution is acco m plis h e d first by neutr ali&a tion to p+ ).< ).* 'ith CaC4 ) and oxidation to precipit a t e the iron/ Cu is remov e d by SX or ce m e n t a t i o n 'ith Un dust for Cu and Cd remov al. Chloride is remov e d by ion exch a n g e , and Un by electro'inning. Table "# sho's a comp a ris o n of me t al recov e ri e s by the t'o proce s s e s . Ta l e $. @ Comp a ris o n of 2etal 8ecov erie s

&SA

3n #C #C

& #* #C #=

Cu =# #< #D

A5 C* C* D*

S ## ##

-" stag e . -3 stag e .

SRL

#$

The reve n u e is slightly high er for the S85 proce s s bec a u s e of incre a s e d %g H Cu recov e r y/ the Pb produc t value high er bec a u s e S 4 free/ and ther e is a credit for + 3 S< = .

(i5ur e 896 S85 proc e s s

(i5ur e 90 @ PS% proc e s s

Chloride Processes Pres e n tly ther e are sev er al oper a tio n s using som e asp e c t of chloride hydro m e t a llurg y, such as ;alconbridg e , 7or'ay/ :uval, ?.S.%./ Elkem Spigerv e rk, 7or'ay/ 5e 7ickel, ;ranc e. Consid er a bl e 'ork has be e n perfor m e d by ma n y on ;eC" ) leaching. Conclusions that may be dra' n from the previou s 'ork@ %dvant a g e s mod e r a t e l y rapid dissolution pyrite unaffect e d mos t of S oxidise d to S < conve n tio n al e,uip m e n t

:isadv a n t a g e s relatively lo' solubility of PbCl 3 and %gCl difficulty of maint aining S4 = 3 control en er g y inten siv e corrosiv e me di a and exp e n siv e ma t e ri als ma n y uncer t ain ti e s in the ne' tech n olog y

The flo'sh e e t is sho'n sch e m a ti c ally in ;igure #". The lead is remo v e d from solution as PbC" 3 cryst als by cooling/ the %g remov e d by ce m e n t a t i o n and the Cu by SX or ce m e n t a t i o n 'ith the Cu. Uinc is recov er e d by SX E!.

(i5ur e 9$ @ Propos e d flo'sh e e t for ferric chloride leaching of bulk comple x sulphid e conce n t r a t e s %nhydro u s chlorina tion proc e s s e s hav e bee n inves tig a t e d at C%72ET. The sch e m a ti c flo'sh e e t is sho' n in ;igure #3 for reaction at abou t )*< < C, oxidation at =<< < C and leach of the calcine 'ith a brine solution. 0ecau s e S 3 C" 3 is produc e d in the reaction of chlorine 'ith the met al sulphid e s , a t'o stag e chlorina tion proc e s s could be consid er e d , as sho'n in ;igure #). The proc e s s 'as prove n to yield high recov e ri e s on 0runs'ick conce n t r a t e s as 'ell as on 2c%rthur 8iver conc e n t r a t e s . +o'ev er S < collection 'as difficult. % me diu m te m p e r a t u r e proce s s 'as dev elo p e d , bas e d on a reac tion te m p e r a t u r e of C<< < C in a chloride bath to ena bl e eas y tran s p o r t by gravity. The conc e p t u al chlorina t or is sho'n in ;igure #=. ;urth e r 'ork 'ould be nec e s s a r y to run a pilot plant, obtain mas s balanc e s , and det er mi n e the technic al and econo mic feasibility.

% comp a ris o n of recov erie s is sho'n in Table 3< belo'. Ta l e $8 @ Comp a ris o n of recov erie s &ro9 e ss ;eCl ) Cl 3 Met al Re9 o = e r e ; ?E@ 3n & Cu A5 (e )*< < C C<< < C #* L## D# ## L## D# #3 #* #$ L#* L#* "<< ##V #CV

(i5ur e 92 @ Sche m a tic flo'sh e e t for tre a t m e n t of UnEPbECuE%g conc e n t r a t e s

(i5ur e 93 @ Possible lo' te m p e r a t u r e chlorina tio n flo'sh e e t

(i5ur e )9 * @ Conce p t u al design of chlorina t or deferrin a t o r react or Sulphur monoc hlorid e is an effective chlorina tin g ag e n t and possible flo'sh e e t s 'ere inves tig a t e d and are sho' n in ;igures #*, #$ 9 #C. The leaching rout e -;igure #C. is und e r pres e n t inves tig a tio n.

(i5ur e 9) @ S 3 C53 H C53 chlorina tion

(i5ur e 9- @ S 3 C53 H ;eCl ) chlorina tion

(i5ur e 9. @ S 3 Cl 3 leaching proc e s s Solution Purification The chloride proce s s e s produc e ess e n ti ally t'o typ e s of solution for purification after cryst alli&ation of PbC" 3 and cem e n t a t i o n. The sche m a t ic flo'sh e e t comp a ris o n s are sho' n in ;igure #D. The approxi m a t e solution feed comp o sition -to SX. are sho' n in Table 3". Ta l e $9 @ Solution ;eed to SX &:ro- H:;ro LoD Me; # Te7 > # Te7 > # )< )< <.= <.= <.= <.= <.<<3 ".* <.<<3 ".* H:;ro (eCl 3 or S 2 Cl 2 "< ".< <.= ")< ".* 3<

3n & Cu (e tot a
l

(e 3 F

The flo'sh e e t for the pyro hydro rout e is sho' n in ;igure #D. %corga P*)<< 'as select e d for the extr ac tio n of copp er 'hile T0P 'as use d for

Un extr a c tion from chloride follo'ed by E! from chloride. The conc e p t u al flo'sh e e t for tre a t m e n t of the ;eC" ) leach li,uor on the S 3 C" 3 leach is sho'n in ;igure ##. The T0P plays an import a n t part in the extr a c tion of Un from chloride solutions . That reag e n t is a useful extr a c t a n t for extr a c tion of ma n y met als from chloride me di a as sho'n in ;igure "<<. Control of acidity and of salt conc e n t r a tio n can be use d to affect ma n y sep a r a tio n s .

(i5ur e 98 @ Chloride proc e s s flo'sh e e t comp a ris o n

(i5ur e 99 @ SX E! circuits for Cu 9 Un

(i5ur e $0 0 @ Conce p t u al ;lo'sh e e t

SECTION %III RECO%ERY O# !RANI!"

Introd7ction The ato mic ener g y indus tr y 'as the prime user of solve n t extr ac tio n for met als sep ar a tio n and recov e r y up to the time of bas e met als recov er y in the late "#$<^ s 'ith the introd uc tio n of the first large copp e r plants coming into prod uc tio n. The recov e r y of uraniu m from ores by using solven t extr ac tio n beg a n in "#** 'ith the use of :E+P% -:%PEX Proces s ., and since "#*C seco n d a r y or particularly the tertiary amin e s -%2EX Proces s . hav e bee n the mos t popular extr a c t a n t s . The tertiary amin e s are selectiv e for uraniu m in the pres e n c e of such impurities as iron, thoriu m, phos p h a t e , rare eart h s . 2olybd e n u m , if pres e n t , 'ill also be extr ac t e d , as 'ell as &irconiu m if pres e n t . The :%PEX proc e s s using :E+P% is not selectiv e, and 'ill co extr ac t ma n y other met als, such as iron, van a diu m , rare eart h s . The gen e r al solve n t extr a c tion flo'sh e e t is sho'n sche m a t ic ally in ;igure "<". The met al be aring proc e s s solution is usu ally fed count e r curre n tly to a flo' of an orga nic solven t fed into a mixing device or cont a c t o r to mix the t'o phas e s . This cont a c t, or extr ac tio n proc e s s , results in the transf er of the me t al species from the a,u e o u s pha s e into the orga nic phas e . >en er ally, mor e than a single stag e of cont a c t 'ill be re,uir e d in order to obtain maxi m u m recov er y of the met al. ;ollo'ing mixing, the phas e s are allo' ed to sep a r a t e or coale s c e . The a,u e o u s pha s e , or raffinat e , is sep a r a t e d from the orga nic pha s e and may be tre a t e d for the recov er y of other value s , recycle d to som e point upstr e a m or do'ns tr e a m of the solven t extr ac tio n proce s s , or disch a r g e d to 'ast e.

(i5ur e $0 $ @ Sche m a tic flo'sh e e t for the recov er y of ?raniu m ;ollo'ing extr ac tio n, the load e d solven t is usu ally cont a c t e d 'ith a scrub solution to remo v e und e sir a bl e impurities from the solven t prior to recov er y of the me t al, in this cas e uraniu m. 1n uraniu m circuits the com m o n impurities on the solven t, usu ally ther e by absorp tion, 'ill be the entr ain e d leach feed li,uor, 'hich 'ill cont ain iron, silica, alu miniu m, and other impurities. 8emov al of thes e , usu ally by 'ater 'as hing, 'ill result in minimu m emulsion and crud form a tion as 'ell as a bett e r final uraniu m produc t. %fter scrub bin g the solve n t pas s e s to the stripping circuit 'her e the uraniu m is recov e r e d in an a,u e o u s solution by cont a c t of the solven t 'ith a suita ble a,u e o u s solution. Such solutions are discus s e d belo'. The result a n t strip solution is tre a t e d in a precipit a tio n circuit to recov e r a uraniu m produc t precipita t e , Ryello' cakeR. The stripp e d solven t is retur n e d to the extr a c tion circuit. 1f nec e s s a r y it may be tre a t e d -e,uilibrat e d . 'ith sulphuric acid prior to extr ac tio n to obt ain maxi m u m sta g e efficiency. Stripping is usu ally consid er e d the revers e to extr ac tio n, and often can be acco m plis h e d by the chan g e in the p+. This is the cas e 'hen extr ac tio n 'ith eith er an amin e or an alkylpho s p h o ric acid has bee n carried out. !ith ion associa tio n and solvatin g syst e m s , such as 'ith the extr ac tio n 'ith T0P from nitrat e or chloride solutions 'her e high salt or acid conc e n t r a ti o n s are re,uir e d for met al extr ac tio n, stripping 'ith 'ater is succe s sf ul. There are sev er al possible strip solutions that can or hav e bee n use d in the recov e r y of uraniu m from the load e d solven t. 1n early circuits, sodiu m carbo n a t e 'as use d. 5ater, controlled p+ stripping 'ith am m o ni a am m o ni u m sulph a t e solution 'as introd uc e d and has bee n the mos t popular. This is in spite of the mos t difficult p+ control nec e s s a r y in order to prev e n t precipita tion of uraniu m and thus the forma tio n of very sta bl e cruds and high solven t loss e s as the res ult. 1n the cas e of syst e m s that hav e molyb d e n u m pres e n t , and ther efor e extr a c t e d 'ith the uraniu m, a sodiu m chloride stripping has bee n succe s sf ul in recov er y of the uraniu m 'ithout co stripping the molyb d e n u m . 1n such situa tio n s the molyb d e n u m is subs e , u e n tl y stripp e d 'ith a sodiu m carbo n a t e solution. 4ther stripping age n t s hav e includ e d sodiu m sulph a t e , or am m o ni u m carbo n a t e . The latter met h o d has the adv a n t a g e of producin g an am m o ni u m uranyl tricarbo n a t e strip solution, 'hich can be subs e , u e n tl y tre a t e d to prod uc e am m o ni u m uranyl carbo n a t e produc t. This produc t can be rea dily conver t e d to ?4 3 , ?4 ) , ?) 4 D , or ?; = . Thus, stripping solution choice should be dicta t e d by the type of produc t and produc t specifications , the ability to control the reaction to minimi&e

crud or precipit a t e forma tio n, the possibility of recycling the barr e n uraniu m solution from precipita tion back to the stripping circuit, the environ m e n t a l impac t due to dispos al of the barr e n strip to tailings impou n d m e n t , and the over all econo mics . Extractants The thre e class e s of extr a c t a n t s use d for uraniu m recov e r y are discus s e d briefly. Acidic extractants The extr ac tio n of me t al s as cations from acidic solution s is very much p+ dep e n d e n t , and ther efor e the degr e e of extr ac tio n is som e ' h a t par allel to the order of the hydrolysis const a n t s . 0eca u s e of this sensitivity to p+ ther e mus t be close control of the acidity in order to reduc e the amo u n t s of co extr a c t e d met al cont a mi n a n t s . The com m o n extr a c t a n t , in the so called :%PEX proce s s , has be e n di 3 ethylh e x yl phos p h o ric acid, often abbr e vi a t e d by na m e s such as@ :E+P%, E+P%, :3E+P%. %s note d abov e and earlier, p+ control is import a n t in this syst e m , and un' a n t e d met als can be extr ac t e d and be a proble m . 4ne such coextr a c t e d met al is iron. This cont a mi n a n t not only occupie s sites on the extr a c t a n t , but it is also extr e m e l y difficult to strip. 2aintaining the iron specie s in a reduc e d oxidation stat e during the extr a c tion sta g e s can minimi&e this co extr ac tio n. 1n addition, bec a u s e met als extr ac tio n into :E+P% is usu ally very fast, the n kinetic differe n c e s bet' e e n uraniu m and iron, the latt er extr ac tin g very slo'ly, can enh a n c e the discrimin a tio n and re(ect the iron. 'asic extractants Tertiary amin e s , such as %doge n )$) -Sher e x Che mic als. or %lamin e ))$ -Cognis Che mic als. hav e bee n the mos t 'idely used anion extr ac t a n t s for the recov e r y of uraniu m from sulph uric acid leach li,uors. !hile thes e extr a c t a n t s are relatively selectiv e for uraniu m, nev er t h el e s s ther e are a fe' other met als that extr a c t much mor e prefer e n ti ally. 1n uraniu m circuits the ma(or impurity that is prefer e n ti ally extr ac t e d to uraniu m is molyb d e n u m , and it can be remo v e d by carbo n a t e stripping after first selectiv ely stripping the uraniu m 'ith a chloride solution. Sever al plant s hav e oper a t e d succe s sf ully 'ith such a proce s s -3).. %lso, oxidi&ed van a di u m if pres e n t 'ill be extr ac t e d and stripp e d tog e t h e r 'ith the molyb d e n u m -3=.. %noth er impurity to the uraniu m circuit could be that of &irconiu m. 1f extr ac t e d , eve n in small ,ua n titie s , it can pres e n t a proble m in the stripping circuit in the form of a crud -3*.. Uirconiu m co extr a c tion can be suppr e s s e d by the addition of phos p h a t e . %lthoug h iron is not extr a c t e d , it can be absorb e d onto the orga nic phas e . This impurity can be remo v e d prior to uraniu m stripping by a 'ater scrub -3) 3$.. 1f ars e nic is pres e n t it 'ill be re mo v e d in a scrub stag e . ;eed solutions having a high chlorine cont e n t 'ill res ult in a decr e a s e in the loading efficiency -3C.. The high chloride ion often arise s from@

the salinity of the proce s s 'at er pu mp e d from the 'ells at the site the use of exce s siv e sodiu m chlorat e additions in the oxidativ e leach the recycle of proc e s s 'at er cont ainin g amo u n t s of chloride, or a chloride elution of an ion exch a n g e resin 'her e the elua t e is to be furth e r proc e s s e d by solven t extr a c tion -E5?EX proc e s s ..

Such solution s ma y be tre a t e d using an alkyl phos p h a t e extr ac t a n t -3D./ by an amin e after first diluting the feed solution/ or by extr ac tio n 'ith T4P4. Syner gis tic extr ac tio n of uraniu m 'ith the tertiary amin e s can be acco m plis h e d 'ith the addition of T4P4 to the solven t to enh a n c e the kinetics. +o'ev er the stripping is difficult -3#.. The T4P4 replac e s the alcohol modifier usu ally use d in such a syst e m . The extr a c tion of uraniu m 'ith a tertiary amin e solution can be repr e s e n t e d as follo's@ from a sulph a t e

3-8 ) 7+. 3 S4 = H ?4 3 S4 = I -8 ) 7+. = ?4 3 -S4 = . ) The effectiv e n e s s of amin e s for the extr a c tion from eith e r sulph a t e or chloride me dia is in the follo'ing order@ Buat e r n a r y L Tertiary L Secon d a r y L Primar y %mines can be used in sulph a t e or chloride me di a 'ithou t a proble m of amin e degr a d a tio n . +o'ev er the amin e s are degr a d e d very ,uickly in the pres e n c e of nitrat e s or nitric acid, or at high oxidation pote n ti al in the leach solutions. This proble m of oxidation degr a d a tio n has occurr e d in sev er al mills 'hen exce s siv e amo u n t s of sodiu m chlorat e oxidan t hav e be e n add e d in the leach, resulting in an E2; of much gre a t e r than $<< m6, and thus amin e degr a d a tio n . 4bviously, good E2; control is nec e s s a r y to prev e n t oxidation and exce s siv e loss e s of the reag e n t . (eutral extractants Tri n butyl phos p h a t e -T0P. has bee n used very ext e n siv ely in the nucle a r field, but prima rily for the refining of the mill grad e uraniu m produc t to high purity uraniu m comp o u n d s such as ?4 ) , ?4 3 , ?; = . 4nly the Palabor a mill in %frica has used the T0P +74 ) proc e s s . The T0P +74 ) syst e m has also be e n use d succe s sf ully for the produc tio n of a refine d &irconiu m met al for nucle ar fuel cladding -)<.. T4P4 has bee n use d in the recov er y of by produc t uraniu m from phos p h o ric acid li,uors.

"odi$iers The addition of a modifying rea g e n t to the extr a c t a n t diluent mixtur e may be nec e s s a r y in order to@ improv e the rate of phas e disen g a g e m e n t follo'ing mixing incre a s e the solubility of the extr a c t e d specie s in the orga nic phas e , and thus prev e n t the form a tio n of third phas e s , and decr e a s e emulsion and ten d e n c y for crud forma tio n

The nec e s sit y for their us e, and the choice of a particular modifier for the syst e m in ,ues tio n, are usu ally only det er mi n e d by tes ts . The mos t com m o n modifiers in uraniu m proc e s sin g hav e be e n T0P for the :E+P% syst e m , and long chain alcohols in the tertiary amin e syst e m . The mos t com m o nly used alcohol has bee n isodec a n ol. +o'ev er ther e see m s to be sufficient indication s from plant oper a tio n s that 'ith continu e d use and recycle of the solven t mixtur e , the isodec a n ol is oxidi&ed to isodec a n oic acid, and ther efor e degr a d e d . %n app a r e n t more sta bl e modifier to oxidation, and 'hich is no' being us ed by som e oper a tio n s is that of tri dec a n ol. 1n the selection of a modifier it mus t be rem e m b e r e d that the diluen t select e d for the particular proce s s ma y, in combin a tio n 'ith a modifier, give ,uite differe n t char a c t e ris tics comp a r e d to anot h e r diluent 'ith the sa m e modifier. Thus any tes ts should be carried out 'ith a modifier in differe n t diluent s . Dil7ents The diluen t is gen e r ally the ma(or part of the solven t pha s e , exce p t in syst e m s in 'hich T0P might be used as the extr a c t a n t . 1n such syst e m s T0P may be use d up to "<<W 'ithout any diluen t being re,uire d, or a modifier. The diluent plays an import a n t part in the extr ac tio n proc e s s -3),)",) 3.. 6arious keros e n e type diluent s hav e bee n used, and the proce s s has bee n gre a tly improv e d by the introd uc tio n of Rtailor ma d e R diluent s 'ith optimu m blend s of alipha tic and aro m a tic cons titu e n t s to enh a n c e not only the pha s e sep a r a tio n char a c t e ris tics, but also the che mis tr y of the solven t extr a c tion and sep a r a tio n proc e s s . ;lash point is no' 'idely recog ni&e d in the choice of a diluen t, and mos t plants select the diluen t 'ith a flash point gre a t e r than "3< < ;. The diluent comp o sition, 'ith reg ar d s to aliph a tic, aro m a tic, par affins and naph t h e n ic cont e n t toge t h e r 'ith the Solvenc y Para m e t e r all hav e a bearin g on the evalu a tio n and selection of the bes t diluen t for a syst e m . The solubility or solvenc y par a m e t e r are ter m s dev elo p e d by the ma n uf a c t u r e r s . 0eca u s e eac h leach solution is peculiar to that particular ore and proce s s conditions , the n the diluen t choice mus t be bas e d on tes ts 'ith select e d modifiers on that particular leach solution. The selection of a diluen t should not be arbitrar y, or be bas e d on costs alon e, or chos e n bec a u s e anot h e r see mi n gly similar oper a tio n is using a particular diluent.

Extraction "edia Sulphate Systems The recov er y of uraniu m from ores by using solven t extr a c tion, beg a n in "#** 'ith the use of :3E+P%, and since "#*C, secon d a r y or tertiary amin e s hav e be e n the mos t popular extr ac t a n t s , particularly the tertiary amin e s in rece n t years . The amin e extr a c tion proce s s 'as dev elop e d by 4ak 8idge 7ation al 5abor a t o r y, Tenn e s s e e , and is kno'n as the %mex proce s s -".. The tertiary amin e is selectiv e for uraniu m in the pres e n c e of impurities such as iron, thoriu m, phos p h a t e , and rare eart h s . The :apex proc e s s -3. using :3E+P%, 'as use d originally for recov er y of uraniu m from ores, but is not as selective for uraniu m as the tertiary amin e in the pres e n c e of impurities such as ferric iron, and rare eart h s . Extraction and selectivity 'ith amin e s dep e n d on the type of amin e use d. +igher loading is note d 'ith the tertiary amin e s , comp a r e d to the secon d a r y amin e s , as is sho' n in ;igure "<3.

(i5ur e $0 2 6 Effect of amin e struct u r e on ?raniu m loading ;igure "<) sho's the effect of p+ on extr ac tio n using a seco n d a r y amin e -).. 1n ;igure "<= is sho'n the effect of sulph a t e conc e n t r a tio n on the uraniu m extr a c tion 'ith the use of a tertiary amin e -).. The %mex proce s s using amin e s has be e n the mor e popular for uraniu m recov er y from tre a t m e n t of ores, due primarily to the bett e r selectivity as comp a r e d to the :apex proce s s using alkylpho s p h a t e s .

(i5ur e $0 3 6 E!!e 9 t o! >H on Uraniu 7 e8tr a 9 t i o n Dit< a s e 9 o n ; a r : a7i n e

(i5ur e $0 * @ Effect of sulph a t e conc. on ?raniu m extr ac tio n 'ith a tertiary amin e Typical of the :apex proce s s for uraniu m recov er y is that of the Ferr 2c>ee plant at Shiprock, 7e' 2exico, sho'n in ;igure "<* -*.. Prior to extr a c tion the clarified feed is cont a c t e d 'ith me t allic iron to reduc e the

ferric to ferrou s. Extraction is in four stag e s of mixer settler s, using a solven t cont ainin g <.l2 :3E+P% plus <."2 T0P in a keros e n e diluent. The flo' ratios are ad(us t e d such that, the load e d solve n t cont ain s approxi m a t e l y #g ? ) < D E5. The load e d solven t is stripp e d 'ith l<W sodiu m carbo n a t e solution in t'o stag e s of mixer settlers , to yield a strip solution of abou t $<g ? ) < D E5.

(i5ur e $0 ) @ Ferr 2c>ee Shiprock plant for ?raniu m 1n Cana d a until the late "#C<Ts, only one mine had oper a t e d a solven t extr a c tion plant for the recov e r y of uraniu m -$.. The initial plant 'as the Port 8adiu m oper a tio n of Eldora d o 7uclear on >rea t 0ear 5ake, 7.!.T., 'hich beg a n using solven t extr a c tion in their plant early in "#*D to produc e )<<<lb ? ) 4 D Eday. Sever al plant s hav e be e n in oper a tio n in the ?.S., South %frica -C., %ustralia -D., and oth er parts of the 'orld using the sa m e proce s s or 'ith slight variations . The proce s s is sho' n sche m a t ic ally in ;igure "<$. %fter leaching the pitchble n d e ore in sulph uric acid and filtration, the clarified solution at a p+ of abou t 3, and cont ainin g ".Cg ? ) < D E5, 'as cont a c t e d 'ith a solve n t mixtur e consisting of <."2 %lamin e ))$ plus * vEo isodec a n ol in SP = Set ;uel diluen t. Extraction took plac e in thre e stag e s of mixer settler s, yielding a raffinat e cont aining abou t <.<<3 g ?) < D E5. Small ,ua n tities of ferric sulph a t e are also extr a c t e d along 'ith the uraniu m 'ith an anion exch a n g e proc e s s . This co extr a c t e d iron 'as not a serious proble m and 'as easily re mo v e d by a 'ater scrub in a

single mixer settler. The Scrub raffinat e cont ainin g the iron can be recycle d -back for mor e scrub bin g. 'ith a blee d being take n off to 'ast e . The scrub b e d solven t, cont ainin g abou t =.*g ? ) < D E5, is cont a c t e d in t'o stag e s of stripping using "<<gE5 sodiu m carbo n a t e yielding a strip solution cont aining 3* to )<g ? ) < D E5. ;ollo'ing stripping the sodiu m uran yl tricarbo n a t e strip solution is precipit a t e d 'ith caus tic to yield a sodiu m diura n a t e produc t grading abou t D<W ? ) < D . The stripp e d solven t, cont ainin g less than <.3g ? ) < D E5, and in the carbo n a t e form, mus t be conv er t e d to the acid form by cont a c t 'ith sulph uric acid in a mixer settler befor e recycling to the first sta g e of extr a c tion.

(i5ur e $0 - @ Port 8adiu m ?raniu m Circuit The +ighlan d ?raniu m oper a tio n in >asp e r, !yomin g, com m e n c e d produc tion in 4ctob e r "#C3 -#.. The uraniu m miner als are uraninit e and coffinite. 2ining is by ope n pit oper a tio n, and feed to the mill at the rate of 3D<< tonsEd a y on a * day 'eek. The ore grad e s approxi m a t e l y ).*lb ?) 4 D Eton ore. The mill circuit consist s of clos e d circuit crus hing, rod mill grinding, acid leaching, count e r curre n t dec a n t a ti o n , solution clarification, including sand filtration, solven t extr ac tio n, precipit a tio n 'ith am m o ni a, 'as hing, de' a t e rin g, and drying. The circuit is sho' n in ;igure "<C. The extr a c tion circuit consists of = mixer settler s. The mixers are polye s t e r lined concre t e , C.*ft s,u ar e x Dft de e p, and the polyes t e r lined settlers are 3<ft x $*ft x Dft de e p. The modified :env er design pum p mix agita t o r is a $ blad e d stainles s ste el impeller.

Solven t consists of a 3.*W solution of %lamin e ))$ in keros e n e , and cont ainin g ".DW isodec a n ol. The solve n t is load e d to abou t 3.*g ? ) < D E5 and the raffinat e , 'hich is return e d to the CC: circuit, cont ain s less than <.<<" g ?) 4 D E5. ?raniu m is stripp e d from the solve n t in = sta g e s 'ith a solution of ")*gE5 -7+ = . 3 S< = at p+ =.* and a te m p e r a t u r e of D*< < ; and flo' of )<gp m. 2ixers are Cft x Cft x Dft dee p, and the settlers "<ft x $*ft x Dft dee p, again polyes t e r lined concre t e . %gitator s are fibre glass cover e d mild ste el. The load e d strip cont ain s 3Cg ? ) < D E5 and the solve n t cont ains less tha n <."g ?) < D E5. Precipit a tion of uraniu m is 'ith anhydr o u s 7+ ) at p+ C.<, in t'o sta g e s , to achiev e a lo' barr e n of less than <.<" g ? ) < D E5. The barr e n is recycle d to stripping, 'ith a blee d to control the -7+ = . 3 S< = build up.

(i5ur e -0 @ +ighlan d ?raniu m oper a tio n % som e ' h a t similar solven t extr a c tion flo'sh e e t is that of Petroto mics , Shirley 0asin, !yomin g, sho'n in ;igure "<D -"<.. Clarified li,uor from leaching in sulphuric acid, and cont ainin g <.C* to "."g ? ) < D E5, is cont a c t e d , in 3 par allel circuits, four stag e s of mixer settlers 'ith %doge n )$= in keros e n e , cont aining tridec a n ol as modifier. The load e d solven t cont ain s 3.*g ? ) < D E5, giving a recov er y of bett e r tha n ##W. Stripping is acco m plis h e d in four stag e s , using am m o ni u m sulph a t e . Precipit a tion is in t'o stag e s , first at p+ $.", follo'ed by $.D to C.<, res ulting in minim al

sulph a t e cont e n t in the precipit a t e . Solven t loss e s 'ere report e d as <.<3 gallons keros e n e , <.<=lbs tridec a n ol, and <.<*lbs of %doge n )$= per ton.

(i5ur e $0 8 @ Petrot o mic s ?raniu m circuit 1n Texas, the Con,uis t a 2ine proce s s e s $,<<<,< < < tons per year of ore gradin g 3 to )lb ?Eton by acid leaching follo'ed by solven t extr ac tio n and precipita tion -"".. The mill, compl e t e d in "#C3, consist s of an agita t e d sulphuric acid leach, count e r curre n t 'as hing of sand s and slimes in thicken e r s , solven t extr a c tion, precipita tion as yello'c ak e , centrifuging, and drying. The flo'sh e e t is sho'n in ;igure "<#.

(i5ur e $0 9 @ Con,uist a ?raniu m oper a tio n

The ore, cont ainin g bent o nit e and clay, is roas t e d to pro mo t e settling and to burn off lignite ma t e ri al, 'hich 'ould caus e high acid and chlorat e cons u m p ti o n in the leach, as 'ell as emulsion in the solve n t extr ac tio n circuit. %fter leachin g, filtration and clarification, the uraniu m bearin g solution is cont a c t e d 'ith %lamine ))$ in 7apole u m =C< in four sta g e s of mixer settlers , 'ith the a,u e o u s the continu o u s pha s e . ?raniu m is recov er e d from the load e d solven t by orga nic continuo u s stripping 'ith am m o ni u m chloride in four uniti&e d fibergla s s reinforc e d plastic mixer settlers ma n uf a c t u r e d by :enver E,uip m e n t Co. %ny trac e s of molyb d e n u m that is extr a c t e d rem ai n s on the solven t, and is remo v e d by stripping 'ith am m o ni u m hydroxid e. The uraniu m is recov er e d from the am m o ni u m chloride strip li,uor by precipit a tio n 'ith am m o ni a gas at p+ C D. %ll tailings and effluen t stre a m s from the plant oper a tio n are impou n d e d . !ater from the tailings pond is retur n e d to the mill for reus e. Ferr 2c>ee 7uclear Corpor a tion oper a t e s nine und e r g r o u n d mine s in the %mbrosia 5ake are a , >rant s, 7e' 2exico. The ore from thes e mine s is proce s s e d in a C,<< < t p d uraniu m mill to produc e Ryello' cakeR -"3.. The clarified leach solution, cont ainin g abou t <.*g ? ) 4 D E5, is cont a c t e d 'ith a solven t mixtur e consistin g of )W %lamine ))$, and )W iso dec a n ol, in a keros e n e diluent. Extraction is achiev e d in four sta g e s of the circular mixer settlers of the :avy Po'er >as design. The settling are a has a cap acity of 3 galEminEft3 in thes e seg m e n t e d circular settler s. The load e d solven t, 'hich cont ain s abou t )g ? ) 4 D E5, pas s e s throu g h four stag e s of stripping, using ".C7 7aCl. The 4E% ratio is "*@". The strip solution, cont ainin g =*g ? ) < D E5 and <.3g 2oE5, is precipit a t e d 'ith 7+ = <+ from a hea t e d solution. 8ete n tio n time for precipita tion is #< minut e s . %fter being thicken e d to abou t *<W solids, the slurry is 'as h e d in t'o stag e s on thre e dru m filters to remov e any entr ain e d sodiu m chloride. The 2ary Fathle e n oper a tio n produc tion during the period ;ebru a r y "#$$ -"3.. The plant pres e n tly proce s sin g "C<< tpd near 2t. 1sa, %ustralia, 'as originally in "#*D "#$), and 'as again reactiv a t e d in is design e d for 3<<< t p d throu g h p u t , and is at a grad e of ".*kg ? ) < D Eton.

The clarified feed to the solve n t extr a c tion circuit is at the rat e of *<<g alE min and cont ains approxi m a t e l y <.Dg ? ) < D E5. The mixers are the pu mp mix design of :avy Po'er >as. % picket fenc e is place d at the entry to the settler from the mixer, and also one acros s the cent e r of the settler. ;our sta g e s of extr ac tio n are us ed in each orga nic continu o u s mixer. The phas e ratio in the mixer has to be controlled at 4E% ".$ to maint ain orga nic continu o u s . The solven t consist s of *W %shland Che mic al %doge n )$=, plus )W nonylalcoh ol in a keros e n e diluent cont aining abou t "*W aro m a tic, and having a flash point of "$< < ;. The solven t is load e d to *.*g ?) < D E5, and the final raffinat e cont ains less tha n <.<<" g ? ) < D E5.

4ne stag e of 'ater scrub bin g remo v e s entr ain e d iron and acid. The uraniu m is recov e r e d from the scrub b e d solven t in = sta g e s of a,u e o u s continu o u s stripping, using am m o ni u m sulph a t e . The p+ is controlled at p+ = by the addition of am m o ni a to stag e 3 and stag e ). The strip a,u e o u s solution is "3 "*g ? ) < D E5, 'hile the stripp e d solve n t cont ain s <."g ?) < D E5. ?raniu m is recov er e d from the strip solution by precipita tion 'ith anhyd r o u s am m o ni a at p+ C. The use of solven t extr a c tion, employin g a tertiary amin e, follo'ing an ion exch a n g e cycle, has be e n us ed by sev er al plant s. This has be e n called the Eluex proc e s s , and is cap a bl e of produc tion of uraniu m comp o u n d s of high purity -")," =.. 1n ma n y plant s, the load e d ion exch a n g e resin has had the uraniu m remo v e d by eluting 'ith a chloride or nitrat e solution. 0eca u s e of the pot e n ti al pollution proble m the nitrat e efflue n t might pres e n t , as 'ell as the possibility of producing a high er purity produc t, the Eluex proc e s s may be com m o n practice in the futur e. This 'ould be particularly true for existing plant s using ion exch a n g e . %n alter n a tiv e to nitrat e elution is elution of the uraniu m 'ith approxi m a t e l y * "<W sulphuric acid, follo'ed by a solven t extr a c tion sep a r a tio n of the uraniu m using a tertiary amin e -").. The Split 8ock 2ill of !est e r n 7uclear, !yomin g, ma d e use of the Eluex proce s s by installing a solven t extr ac tio n circuit in their existing resin in pulp plant in "#$$ -"*.. % sulphuric acid solution cont ainin g "3<g + 3 S< = E5 is used to elute the uraniu m from the resin. The preg n a n t elua t e cont ains "3 "=g ?) < D E5, at a flo' of *< $<gp m . ?raniu m is extr ac t e d in four stag e s of mixer settler s, using a $W tertiary amin e in keros e n e , and cont ainin g ) =W isodec a n ol. The barre n raffinat e from the last sta g e is pum p e d to a settler for remo v al of any rem ai ning solven t, and the n ad(us t e d to "3<g + 3 S< = E5 for recycle to the ion exch a n g e circuit. ?raniu m is recov e r e d from the solven t in four sta g e s by controlled p+ stripping 'ith "3<g -7+ = . 3 S< = E5 solution. %nhydro u s am m o ni a is add e d to control the p+ at =.* and ).* in the first and seco n d stag e s resp e c tiv ely. The strip li,uor, cont aining approxi m a t e l y ))g ? ) < D E5, is ad(us t e d to p+ C.< 'ith gas e o u s am m o ni a to precipita t e the uraniu m. The flo'sh e e t is sho'n in ;igure ""<. %ny molyb d e n u m extr a c t e d is remo v e d from the solve n t after stripping of uraniu m, using sodiu m carbo n a t e as the strip solution.

(i5ur e -$ @ !est er n 7uclear Split 8ock ?raniu m oper a tio n %t 0uffelsfont ei n, South %frica, a tertiary amin e 'as used to extr a c t the uraniu m in a pilot plant oper a tio n, from the "<W sulphuric acid eluat e from ion exch a n g e proce s sin g -"$.. This proce s s , kno'n as the 0ufflex proce s s , 'as subs e , u e n t l y installed at the +armo n y >old 2ine in South %frica -"C.. Except for polythion a t e , the poison build up and gen e r al perfor m a n c e of resin elute d 'ith "<W sulph uric acid are no 'ors e than thos e of resin elut e d 'ith nitrat e . The use of sulphuric acid elution follo'ed by solven t extr ac tio n, results in a higher purity produc t at lo'er costs. The main saving in cost is due to the elimin a tion of nitric acid. The sulph uric acid us ed for elution is subs e , u e n t l y re use d in the leachin g proce s s -"C.. %mmonia cons u m p ti o n is less than that cons u m e d in the nitrat e elution proc e s s and its cost is ther efor e lo'er. %fter elution 'ith "<W + 3 S4 = , the uraniu m is extr a c t e d in four sta g e s of mixer settlers 'ith *W %lamine ))$ in keros e n e , cont ainin g 3W isodec a n ol. %n after settler is used to recov er any entr ain e d so"v e n t before retur ning the raffinat e to the leaching circuit. ;our sta g e s of scrub bin g, using 'at er and a small amo u n t of am m o ni u m hydroxid e solution remo v e s impurities such as iron, silicon, ma g n e s i u m , and calciu m from the load e d solve n t. Stripping is acco m plis h e d in four stag e s of mixer settlers , using "*W -7+ = . 3 S< = at p+ C.<, *.<, and ).* by the addition of 3.*2 7+ = <+ solution. The stripp e d solven t is reg e n e r a t e d , in a one stag e mixer settler, 'ith a solution mixtur e cont aining sodiu m carbo n a t e and sodiu m hydroxid e to maint ain the p+ at D.*. This proce d u r e also remov e s thiocya n a t e as 'ell as other poisons pres e n t . The reg e n e r a t e d solve n t in the free bas e form is pum p e d to the solve n t stora g e tank for re us e.

?raniu m is recov e r e d from the strip solution by precipit a tion at p+ C.< 'ith am m o ni a gas. The uraniu m produc t produc e d by this rout e app a r e n tl y met mos t of the nucle a r grad e specification s. %lso in South %frica, the Purlex proc e s s 'as dev elo p e d subs e , u e n t to the 0ufflex proc e s s -"D.. The +armo n y mine ad a p t e d the 0ufflex proce s s , but bec a u s e the Purlex proce s s prov e d more econ o mic al, the 0ufflex proce s s 'as nev er 'idely ada p t e d . The Purlex proce s s is similar in ma n y asp e c t s to the %mex proce s s used in the ?.S.%., Cana d a , and else' h e r e . The ess e n ti al differe n c e s are in the scrub bin g and in the prod uc tio n of the final produc t. The diagr a m m a t i c flo'sh e e t is sho'n in ;igure """. Solvent consist e d of * vEo %lamine ))$ in keros e n e , also cont ainin g 3 vEo isodec a n ol. :ue to fungus gro't h, the isodec a n ol 'as replac e d 'ith )*W Solves s o "*< diluent. Comp a ris o n test s 'ith %doge n )$= sho' e d it to be as satisfact o r y as %lamin e ))$.

(i5ur e $$ $ @ Purlex ?raniu m flo'sh e e t The leach solution cont ains <.)g ? ) < D E5, ).*g + 3 S< = E5, "* 3<g S4 = E5, and 3<g SC7E5. Chloride, up to as muc h as <.DgE5 can also be pres e n t . Extraction is in four stag e s of mixer settler s, using a <."2 solution of am m o ni u m hydroxid e in sta g e s ", 3, and =. 1n the third sta g e , "<W sulphuric acid 'as used to remo v e iron. The uraniu m is recov e r e d by controlled p+ stripping in four sta g e s 'ith am m o ni u m hydroxid e.

1n order to prev e n t crud forma tio n deioni&e d 'ater is use d to prep a r e the am m o ni u m hydroxid e strip solution, consistin g of =W 7+ ) "*W -7+ = . 3 S< = . The stripping is controlled at p+ ).# =.), =.C =.#, and *." *.). +ydrolysis occurs in the rang e p+ ).* to $.*. %mmo niu m sulph a t e forms and is recycle d after the precipita tion of am m o ni u m diura n a t e 'ith gas e o u s am m o ni a at p+ C.). %pproxim a t e l y CD<<lbs of ?) < D are produc e d daily. %gain, as in the 0ufflex proce s s , the stripp e d solve n t is reg e n e r a t e d for re use by tre a t m e n t 'ith a $W sodiu m carbo n a t e solution at a rat e of <.3*g alE min. The p+ is controlled at D.* by the addition of "<W caus tic sod a solution. 4rganic continuo u s 'as maint ain e d throu g h o u t the oper a tio n in order to minimi&e solven t loss e s. 1n South %frica, eight of the t'elve uraniu m produc e r s no' oper a t e Purlex circuits, 'hile t'o plant s use the 0ufflex proc e s s . The rem ai ning t'o plant s use resin ion exch a n g e . (itrate Systems 7itric acid has also bee n use d for the tre a t m e n t of uraniu m ores, particularly thos e of the lo' grad e and comple x type of miner alo g y. There is at pres e n t one kno'n plant using nitric acid@ the Palabor a mine in South %frica. The Palabor a 2ining Comp a n y 'ent on stre a m in "#C", proce s sin g the gravity conc e n t r a t e d tailings from a copp e r conce n t r a t o r oper a tio n -"#.. ;eed to solve n t extr ac tio n cont ains , in gE5, )< =< ? ) 4 D , "3< "=< Th4 3 and D< "<< free +7< ) . The uraniu m -and som e thoriu m. are extr ac t e d in a six stag e mixer settler oper a tio n using "<W T0P in Shellsol 8. Co extr a c t e d thoriu m is re mo v e d by scrub bin g 'ith uran yl nitrat e , in four sta g e s . %ll mixer settlers in the plant are constru c t e d of stainle s s )"$5. Eight stag e s of 'ater stripping, at abou t =< < C, res ults in a solution cont ainin g )< *<g ?) < D E5. The stripp e d solven t is 'ash e d 'ith sodiu m carbo n a t e , in one stag e and then a one stag e acid pre e,uilibra tio n befor e recycling. ?raniu m is recov e r e d from the strip solution as am m o ni a diura n a t e , by the addition of gas e o u s am m o ni a . The calcine d produc t cont ain s less tha n <.$W thoriu m on a ? ) < D basis. The thoriu m, in the raffinat e after uraniu m recov e r y, is tre a t e d 'ith sulphuric acid and disch a r g e d . The analys e s of the calcine d uraniu m oxide are sho'n in Table 33. Ta l e 20 @ Typical ?raniu m oxide at Palabor a Ele 7 e n t >> 7 Ele7 e n t Al 3* Mn As O) Mo / <.) "i /i O" & Co O" S C; <.) Sn Cu # Si (e $< , M5 =< 3n

>> 7 Chloride Systems

O"

<.*

O"

"C

O)

)<<

O"

"<

Conve n tio n al proce s sin g of uraniu m ores involves leaching 'ith eith er sulphuric acid or alkaline carbo n a t e solutions . 0oth proc e s s e s , altho u g h effective for uraniu m, res ult in tailings cont ainin g ess e n ti ally all the radion uclid e s , such as 8a 33$ and Th 3)<. %n altern a tiv e proc e s s flo'sh e e t has bee n dev elop e d 'her e b y the ore or conc e n t r a t e is leach e d in hydroc hloric acid, solubili&ing all the radionu clid e s -)).. The uraniu m is recov er e d by solven t extr ac tio n 'ith a 3.*W solution of T4P4 in Shell "=< diluent, and the solve n t is scrub b e d to remo v e impurities using a uraniu m chloride solution. 0eca u s e T4P4 is difiicult to strip for uraniu m recov e r y, a ne' stripping tech ni, u e 'as dev elop e d using a solution mixtur e consisting of *W + 3 S< = H *W + 3 < 3 . ;inally the stripp e d solven t is scrub b e d 'ith 32 7aCl to remov e sulph a t e prior to recycling the solven t to the extr a c tion circuit. The chloride solutions 'ere derive d from the leaching of uraniu m ores by eith er +Cl, or by a chlorination roas t follo'ed by a dilute +Cl leach. The analys e s of a typical lo' grad e ore is given in Table 3), and the typical chloride leach li,uor comp o sition res ulting from the chloride leachin g is sho'n in Table 3=. The sche m a t ic flo'sh e e t is sho' n in ;igure ""3. Ta l e 2$ @ Typical Elliot 5ake 4re %nalysis E <."= <.<)$ 3.CC 3.DC )D.= ).$ <."* =<<pCiEg Si HCl (RE
E

<.<C* "=.= )C3< pCiE 5

U T< (e S Si Al R#E# Ra

Ra22 -

Ta l e 22 @ 5each Solution %nalysis gE5 5BL <.$* <.3< ).<# 3.))

U T< (e TOTAL (e 2F

(i5ur e $$ 2 @ Sche m a t ic ;lo'sh e e t . Solution "ining Solution mining follo'ed by purification is anot h e r typ e of uraniu m proce s sin g to arise in rece n t year s. 0oth sulphuric acid and carbo n a t e syst e m s are being employe d . The %gne' 5ake 2ine in 4ntario, Cana d a , com m e n c e d oper a tio n in "#C$ follo'ing succ e s sful benc h and pilot 'ork by the labor a t ori e s of C%72ET, 4tta' a -3<., and the subs e , u e n t testin g of solution mining on a surfac e stockpile and in an und er gr o u n d stop e -3<.. The plant has a cap acity of " million tpy of ? ) < D at a cost of abou t [)C million -3".. The oper a tio n mak e s use of in situ und e r g r o u n d leaching and surfac e leaching of blast e d ore, using a bact e rially assis t e d -thiob a cillus ferro oxida n s . ferric sulph a t e leach -33.. The clarified leach solution is proce s s e d by continu o u s ion exch a n g e , using a +imsley column. The resin is elut e d 'ith sulph uric acid and the elua t e is tre a t e d in an eluex circuit using a tertiary amin e for the solven t extr a c tion recov er y and purification of the uraniu m.

;ollo'ing stripping, am m o ni a. Re$erences

the

uraniu m

is recov er e d

by precipit a tio n

'ith

". Crous e, :.S., and 0ro'n, F.0., 4875 3C3<, 5abora t or y, 4ak 8idge, Tenn e s s e e , "#*#.

4ak

8idge

7ation al

3. 0ro'n, F.0., and Colem a n , C.;., Solven t Extraction in 4re Proce s sin g, Progre s s in 7uclear Energy, Series 111, 3, pp. ) )=, Pub. Perga m o n Press -"#*D.. ). Cole m a n , C.;., 0ro'n, F.0., 2oore, S.>., and Crous e, :.S., 1nd. Eng. Che m., *<, pp. "C*$ "C$3, "#*D. =. 0lake, C.%., 0aes, C.;., 0ro'n, F.0., Cole m a n , C,;. and !hite, S.C., in Proce e di n g s of the Secon d ?nited 7ations 1ntern a tio n al Confer e n c e on the Peac eful ?ses of %tomic Energy, >enev a , "#*D, 6ol, 3D, pp, 3#D 3#D. *. +arra h, +.!., :eco Trefoil, Spring 1ssue, "#$#. $. Trembl a y, 8,, and 0ram' ell, p., Trans. of the Can. 1nst. 2in. and 2etall., $3, 7o. ==, pp. == *) -"#*#.. C. 5loyd, P.S., Sour. South %frican 1nst. 2in. and 2etall., 2arch, "#$3, pp. =$* =D#. D. 0ellingh a m , %., Proce e din g s of the %us. 1.2.2., "#D, pp. D* ""3, "#$". #. %bra m o, S.%., and 5o'ings, S.!.+., R?raniu m Proce s sin g at Exxon^ s +ighlan d 4per a tio nR, pres e n t e d at Symp o siu m on Solvent 1on Excha n g e , %1ChE, Tucson, %ri&ona, 2ay, "#C). "<. >arb ella, E.S., :eco Trefoil, !inter 1ssue, "#$D $#. "". Engine e rin g and 2ining Sournal, %ug. "#C3, pp. C= CC. "3. Privat e com m u nic a tio n. "). Simard, 8., >ilmore, %.S., 2c7am a r a , 6.2., Parson s , +.!., and Smith, +.!., Can. S. Che m. Eng., )#, 7o. $, pp. 33# 3)= -"#$".. "=. ;isher, S.!., and 6ivyurka, %.S., 1on Excha n g e in the Proce s s 1ndus trie s, Pub. Society of Che mic al 1ndus tr y, 5ondon, "#C<, pp. "$) "$C. "*. :eco Trefoil, 2ay Sune Suly, "#$C.

"$. ;aure, %., ;inney, S., +art, 0.P., Sorda a n, C.5., 6an +eerd e n , :., 6il(oen, E.0.,.8obins o n, 8.E., and 5loyd, P.S., in Proce e di n g s of Panel on Proces sin g 5o' >rad e ?raniu m 4res, 1%E%, 6ienna, "#$C, pp. ""# "=". "C. Cross, 8., S. South %frican 1nst. 2in, and 2etall,, 7ov. "#$D, pp. "#$ 3<". "D. Tunley, T.+., and ;aure, %., RThe Purler Proces s R pres e n t e d at %nnual 2eeting, %12E, !ashingt o n , ;eb. "#$#. "#. >eorg e , :.8., and 8oss, S.8., in Proce e din g s of Panel Proce s sin g 5o' >rad e ?raniu m 4res, 1%E%, 6ienna, "#$C, pp. 33# 3)3. 3<. 2cCree d y, +.+., R0act erial 5eaching to be %pplied to a 7e' Cana di a n ?raniu m 2ineR, pres e n t e d at a Coordin a tio n 2eeting of the 1%E% on 0acterial 5eaching 8ese a r c h, Coven try, ?.F., :ec. ") "*, "#C$. 3". Cana di a n 2ining Sournal, p. ##, %pril "#$$. 33. ?raniu m 4re Proce s sin g "#C* -1%E%.. Proce e din g s of an %dvisory >roup 2eeting,

3). 8itcey, >.2. and %shbrook, %.!., in Solven t Extraction Principles and %pplications to Proces s 2etallurgy, 3 vol., Pub. Elsevier Scientific Publishing Comp a n y, %mster d a m , "#C#, "#D3. 3=. Sialino, E., 2ignot, C., 2ichel, P., and 6ial, S., in Proce e din g s of 1ntern a tio n al Solvent Extraction Confer e n c e , 1SEC^CC, Toronto, PP. *#3 *##. 3*. 8itcey, >.2., `Crud in ?raniu m Solvent Extractiona, Proce e di n g s of the "=th 1ntern a tio n al 2ineral proce s sin g Congr e s s , Toronto, 4ctob e r "#D3 -C12.. 3$. The Fey 5ake Proce s s . Pres e n t e d by Staff of Fey 5ake 2ining Corp. and Sherritt >ordon 2ines 5td., at C12 Confer e n c e of 2etallurgist s, +alifax, 7ova Scotia, %ugus t, "#D<. 3C. 0ellingh a m , %.r in Proce e di n g s of the %us. 1.2.2.,vol. "#D, pp. D* ""3, "#$". 3D. 8itcey, >.2., Price, F.T., !ong, E.!., R:evelop m e n t of an Eluex Proces s for the Treat m e n t of +igh Chloride ?raniu m Eluat e s R, pres e n t e d at "#D" %nnual Cana di a n ?raniu m Produc e r s 2etallurgic al Com mitt e e 2eeting, Sask a t o o n , 2ay, "#D". 3#. C%72ET, Energy 2ines 9 8esourc e s , 4tta' a, unpu blis h e d dat a.

)<. Craige n, !.S.C., Soe, E.>., 8itcey, >.2., Can. 2et. Buart e rly, C12, vol. #, pp. =D* =#3, "#C<. )". 8itcey, >.2., and 5ucas, 0.+., Proce e din g s of 1ntern a tio n al Solvent Extraction Confer e n c e , 1SEC^C=, pp. 3=)C 3=D". )3. Shelley, P. and Buan, C., RPerfor m a n c e of Sever al 7e' 7il %roma tic :iluent s in the 8ecov er y of Copper, ?raniu m and 8are EarthsR, pap e r pres e n t e d at 1ntern a tio n al Solven t Extraction Confer e n c e , Fyoto, Suly "##<. -1SEC^#<.. )). 8itcey, >.2., !ong, E.!., Solvent Extraction of ?raniu m chloride leach li,uor, Paper pres e n t e d at %12E, "#D=. from a

SECTION IX

SEPARATION O# NIC<E = CO-A T

Process O0tions !sin* Solvent Extraction $or the Processin* o$ aterites istorical Co*(i Separation &y Solvent Extraction 1n Table 3* are listed som e 7ickel solve n t extr ac tio n plant s. The sep a r a tio n of nickel and cobalt 'as, for ma n y year s, acco m plis h e d by a series of labour inten siv e and exp e n siv e step s such as precipit a tion s , cryst alli&ation s , re dissolution and recrys t allis a tio n. 1t 'as not until the early "#$<^ s that the possibility of using a rea s o n a bl y ne', indus trial prove n proce s s of solve n t extr a c tion could be consid e r e d for sep a r a tio n and recov e r y. The succ e s s of uraniu m proc e s sin g initiat e d in the "#*<^ s , gav e res e a r c h e r s the incentiv e to find oth er use s for this ne' unit oper a tio n. So as the uraniu m plant s 'ere in their seco n d gen e r a tio n of installations in the "#$<^ s , ma n y pot e n ti al me t al application s 'ere exa mi n e d . Copp er 'as one, and beca u s e of the environ m e n t a l cons tr ain t s at that time impos e d on smelt e r s , copp er very ,uickly bec a m e the initial candid a t e to follo' uraniu m. 4ther factors such as availability of scrap iron for cem e n t a ti o n , and the comp a r a tiv e costs of SX E! over ce m e n t a t i o n and precipita tion proc e s s e s ma d e the proce s s easily acce p t a bl e , and so the first copp e r plant ca m e on stre a m in "#$# to produc e electro' o n copp er. 4ther met als of inter e s t at that time includ e d that of nickel and cobalt. :uring the "#$< "#C* period, res e a r c h group s in Cana d a -8itcey, "#$D, "#C* b/ Thornhill, "#C"., ?S% -Eliason, "#C=/ Cook, "#C "., 5SF -;letch e r, "#$=, "#$#., 8ussia ->indin, "#$< a , b/ >indin "#$"/ 0obikov, "#$)., +olland -Spit&er, "#$$., 1srael -0lumb e r g , "#$=., 7or'ay -!igstol, "#C"., 0elgiu m -;letch e r, "#C)., S'ed e n -%ue, "#C". and ;ranc e -0o&ec, "#C=. 'ere eng a g e d in the dev elop m e n t of tech n olog y that 'ould incorpor a t e solven t extr ac tio n. 5ater, as tech n olog y 'as dev elo p e d , and solven t extr a c tion as 'ell as the possible application bec a m e mor e acce p t a bl e , oper a tin g plant s 'ere installed in 0ra&il, ;inland, China -pers o n al com m u nic a tio n., South %frica -Clem e n t e , "#D<., Sapan -%ndo, "#C)/ Suet s u n a , "#D<., and %ustralia -8eid, "##).. :uring that period, ess e n ti ally all the feeds to solve n t extr a c tion 'ere eith er solutions from the leaching of sulphid e ores, sulphid e precipit a t e s , mat t e , scrap, or the tre a t m e n t of blee d stre a m s from anot h e r proce s s . The feed solutions 'ere eith er + 3 S4 = , or +Cl, or alkaline sulph a t e or carbo n a t e . Thus, bec a u s e of the abun d a n c e of sulphid e s , ther e has not bee n much inter e s t in the proc e s sin g of leach solution s, resulting from tre a t m e n t of laterit e s , by solve n t extr a c tion for the sep a r a tio n of nickel and cobalt. 4ne inves tig a tio n, suppor t e d by the ?nited 7ations, 'as on the 0urun di,

%frica laterit e s in "#C= C* -8itcey, "#C* a .. The proce s s 'as subs e , u e n t l y pilote d by ?4P in %ri&ona -?4P, "#CD. during the ple of years . +o'ev e r, in the period 'hen this took plac e, bec a u s e of the lo' price of nickel and cobalt at that time, and the cost of the infras tr uc t u r e re,uire d in a land locked countr y that had rece n tly gon e throu g h intern al strife, the pro(ect 'as not take n to prod uc tio n. 2ore rece n tly ther e has bee n an incre a sin g inter e s t in the proc e s sin g of nickel laterit e s and the application of solve n t extr a c tion. This start e d in Cuba -pers o n al com m u nic a tio n., and pres e n tly ther e is inten s e inter e s t particularly in %ustralia, 'her e a nu mb e r of depo sits are in various sta g e s of dev elo p m e n t . 1n the pas t, the plants using solven t extr ac tio n for the recov e r y of cobalt and nickel hav e proce s s e d ma n y type s of feed s, including solution s resulting from ores, conc e n t r a t e s , precipita t e s , mat t e s , various scra p mat e ri als, and 'ast e efflue n t s for \value addingT and for environ m e n t a l control. +hy do ,e Choose Solvent ExtractionThere are consid er e d and cobalt includ e the X X X X X X X a num b e r of rea s o n s 'hy solven t extr ac tio n should be for application to the tre a t m e n t of solution s cont aining nickel toge t h e r 'ith the att e n d a n t impurities -8itcey, "#D3.. Thes e follo'ing@

re,uir e m e n t to sep ar a t e t'o che mic ally similar me t al s, high purity produc t s of nickel and cobalt are de m a n d e d , desire to improv e a pres e n t produc tio n plant, to decr e a s e rea g e n t costs, to decr e a s e ma n p o ' e r costs, to decr e a s e ener g y cons u m p tio n, to decr e a s e the environ m e n t a l impac t due to forme r proce s sin g tech n olo gi e s .

There are no' sev er al hundr e d solven t extr ac tio n plants throu g h o u t the 'orld tre a tin g a variety of me t als over a 'ide rang e of flo' volum e s , from perh a p s a fe' litres per hour, as for gold refining, to sev er al thous a n d s of litres per minut e in the cas e of the large copp e r oper a tio n s . Extractants for Co*(i The com m e r ci ally availabl e extr ac t a n t s are sho' n in Table 3$. %lthoug h ther e are som e similarities 'ithin each extr ac t a n t class -e.g. cationic, and chela tin g. nev er t h el e s s the choice 'ill be dicta t e d by@ X X X other comp o n e n t s in the feed solution, the anion and anionic stre n g t h / the acidityE alkalinity and, the desire d final produc t.

Table 3C sho's the gen e r al order s of selectivity, in decr e a s i n g selectivity. Som e inform a tio n is from actu al syst e m s , 'hile other dat a are from the dat a she e t s of the ma n uf a c t u r e r .

Ta l e 2- 6 Cobalt 7ickel Extract a n t s 8E%>E7T :E+P% P 3<= PC DD% P *<C lon,u e s t D<" Cyan e x 3C3 Cyan e x )<3 )<" 1::P% 6ersatic "< 51X -various. %corga -various. %lamine ))$ -%. %doge n )$),) $ = -%. T0P -%. -0. TAPE Phosp h oric %cid Phos ph o nic %cid Phos ph o nic %cid Phos ph o nic %cid Phos ph o nic %cid Phosp hinic %cid Phosp hinic %cid Sulphur Subs titu tion 1sodod e c ylp h o s p h a t a n i c %cid Tertiary 2onocar b o nlic %cid Chelating Chelating Tertiary %mine Tertiary %mines Tri 0utyl Phos ph a t e S?PP51E8 %lbright 9 !ilson, +oech s t, :aihac hi Shan g h ai Che mic al Plant :aihac hi Chines e %lbright 9 !ilson CATEC Cana d a CATEC Cana d a 8ussia Shell Che mic als C4>71S -+enk el. 1C1 Uen ec a C4>71S -+enk el. !1TC4 6arious

;or use from high +Cl andEor chloride conce n t r a tio n s ;or use from high acid stre n g t h +Cl or +74 ) solution s

%ll the other s in the list oper a t e in the p+ rang e of abou t = C. %lthoug h thes e sa m e extr ac t a n t s are cap a bl e of extr a c tion from high p+ solutions, the extr a c t a bility decr e a s e s as the both the p+ and the anion conc e n t r a ti o n are incre a s e d . Ta l e 23 .6 >ener al 4rders of Selectivity. :E+P% PC DD%, P *<C, 1on,u e s t D<" Cyan e x 3C3 Cyan e x )<", )<3 6ersatic "< %mines T0P ;e L Cu L 7i ;e L Cu L 7i ;e L Cu L 7i ;e L Cu ;e L Cu L 2g Un L ;e ;e L Un L Un L Ca L 2g L Co, 2n L Un L Ca L Co, 2n L 2g L Un L Co, 2n L 2g L Ca L Co L 2n L 7i L Ca L 2g L Un L 7i L Co L 2n L Ca L Cu L Co L 2n L 7i L Cu L Co L 7i

The order of selectivity of CoE7i 'ith the alkylpho s p h a t e s incre a s e s in the order@ phos p h o ric O phos p h o nic O phos p hinic !ith the exce p tion of the 6ers atic "< extr ac t a n t , all extr ac t Co prefer e n ti ally to 7i. The revers e occurs 'ith 6ersatic, exce p t at p+ abov e C.* 'her e Co is gen e r ally prefer e n ti ally extr ac t e d to 7i, at p+ D.* optimu m . !ith the use of chela tin g extr a c t a n t s , unles s Co is in the Co )H stat e it 'ill be extr ac t e d prefer e n ti ally to 7i. %nd if extr a c t e d in the reduc e d form, unles s it is kept reduc e d it 'ill oxidi&e in the orga nic phas e and be virtu ally non stripp a bl e. +o'ev er, the chela tin g extr ac t a n t s are exc ellen t 7i extr a c t a n t s . ?sing the solvatin g extr ac t a n t s or the amin e s , 'hile cobalt is extr ac t e d from high acid conc e n t r a tio n, and in the cas e of the use of T0P or amin e s , the addition of thiocya n a t e to the a,u e o u s pha s e improv e s the extr a c tion, the sep a r a tio n over nickel is high. 7ickel is not extr ac t e d by eith er class of extr a c t a n t s . !ith the amin e s and the solvatin g extr a c t a n t s , both the acid and the anion conce n t r a ti o n 'ill influenc e the order of extr a c tion. %lso, the relativ e conc e n t r a tio n s of the me t al s in solution can affect the order.

E8tra 9 ti o n !ro 7 A9i;i9 Me;i u 7 !l-yl Phosp h oric !cid This 'as the first Co 7i sep a r a tio n pro ces s using an alkylphos p h a t e ex t ract a n t -8itcey, "#$D, "#C* b.. 1n that proc e s s , use d in the early "#$<^ s , and sho' n in ;ig. ""), the control of the e,uilibriu m p+ at abou t p+ * $ rang e 'as by pre e,uilibra tio n 'ith eith er 7a 4+ or 7+ = 4+. -%ctually any alkaline rea g e n t can be us ed, or a met al salt that 'ill be replac e d by the me t al being extr ac t e d , eg., Co.. The introdu c tion of a purification scrub 'as also novel. %lso the proc e s s , 'hich ran for a time in a shut do'n uraniu m refinery, used a single siev e plat e puls e column in both extr a c tion and scrub, thus providing ma n y theor e tic al stag e s to achiev e high purity. 1ncre a s e d Co 7i sep a r a tio n 'as achiev e d at elev a t e d te m p e r a t u r e s . 1n ;ig ""= 9 ""* are sho'n extr a c tion curves for sev er al met als by :E+P%, and the effect of te m p e r a t u r e -;ig. ""$./ extr a c tion column profile -;ig. ""C. and scrub bin g dat a -Table 3D.. Pyrites Comp a n y in the ?S% subs e , u e n tl y us ed the proc e s s for the tre a t m e n t of scrap -Cook, "#C"., and the 2atth e y 8ust e n b u r g 8efiners Comp a n y in South %frica are using the sa m e proce s s for recov e r y and sep a r a tio n of Co and 7i -Clem e n t e , "#D<.. The subs e , u e n t plants using the improv e d phos p h o nic or phos p hinic acids ma d e use of this original proce s s flo'sh e e t , for the che mis tr y 'as the sa m e , the only differe n c e being the incre a s e d Co 7i sep a r a tio n factor 'ith the phos p h o nic acid and subs e , u e n tl y a furth er improv e m e n t 'ith the phos p hinic acid. Phosph o nic !cids ;ollo'ing the succe s s of the use of :E+P% for the sep ar a tio n of Co 7i from acid leach solution s, the dev elop m e n t of the phos p h o nic acid extr a c t a n t by :ihachi and 7ippon 2ining in Sapan -PC DD%. en a bl e d an improv e d perfor m a n c e in the 7ippon 2ining plant for the recov e r y of Co and 7i. %lthoug h the abov e pat e n t e d -8itcey, "#$D/ "#C* b. proce s s 'as licens e d to 7ippon 2ining in Sapan, by the time that plant 'as constru c t e d in "#C* an improv e d alkylpho s p h a t e 'as available, a phos p h o nic acid kno'n as PC DD% that provide d for an incre a s e d discrimin a tion over 7i. So 7ippon -%ndo, "#CC. use d :E+P%, follo'ing iron remov al by precipita tion, for the remo v al of Un impurity. Co 'as the n extr a c t e d 'ith PC DD%, at abou t p+ *.*. The raffinat e 'as ad(us t e d in p+ to abou t D.* and the 7i extr ac t e d 'ith 51X $*7. The flo'sh e e t is sho' n in ;ig. ""D. %noth e r phos p h o nic acid extr ac t a n t that 'as dev elo p e d abou t the sa m e time is the 1on,u e s t D<" by %lbright !ilson in the ?S%. The extr ac tio n prop e r ti e s are similar to the PC DD%. %n earlier phos p h o nic acid that 'as dev elo p e d 'as kno'n as S2E ="D by Shell Che mic als in %mst er d a m .

Phosphinic !cids The subs e , u e n t dev elo p m e n t of the phos p hinic extr ac t a n t s by CATEC -e.g., Cyan e x 3C3. has res ult e d in improv e d sep a r a tio n factors for the Co 7i sep ar a tio n. The Co 7i sep a r a tio n incre a s e s in the order phos p h o ric O phos p h o nic O phos p hinic at *< C. 2ost Co plants are no' using that rea g e n t . The Cytec extr ac t a n t s are given in Table 3#. ;ollo'ing the Cyan e x 3C3, the extr ac t a n t s Cyan e x )<" and Cyan e x )<3 bec a m e available. Thes e extr a c t a n t s are the res p e c tiv e mono t hio and dithio analog s of Cyan e x 3C3. The extr ac tio n e,uilibria of Cu -""., Co -""., 7i -""., Un -""., ;e -""". by <." 2 Cyan e x 3C3, )<", and )<3 are sho'n in the follo'ing pag e s . The p+ at 'hich extr a c tion of each met al occurs decr e a s e s in the order. phos p hinic acid O thiopho s p hinic acid O dithiop h o s p hi nic acid 7ickel is the mos t significantly affect e d by incre a sin g the sulph ur subs tit u tion of the phos p hinic acid/ iron extr a c tion is the leas t affect e d -Prest o n.. Stripping of Co is easie s t from the Cyan e x 3C3. The flo'sh e e t for use of the phos p hinic acid extr a c t a n t s is similar to that originally dev elo p e d for the phos p h o ric acid extr a c t a n t -;ig "").. Some dat a are sho'n in ;ig. ""#," 3 <. % comp a ris o n bet' e e n the Cyan e x 3C3, )<", and )<3 are given in ;ig. "3" "3). ?se of the Cyan e x )<" me a n s that Co and 7i are co extr ac t e d , and a stron g acid co strips the met als . % secon d solven t extr a c tion circuit 'ith anot h e r rea g e n t is re,uir e d for sep a r a tio n of Co from 7i. 1f stron g +Cl is use d, the n a tertiary amin e or T0P may be consid e r e d . This 'ould be similar to the plants that hav e extr ac t e d from stron g chloride me di a -e.g. ;alconbrid g e and other s .. Car.ox ylic !cids $@ersatic #2 % There hav e bee n nu m e r o u s inves tig a tio n s , proce s s flo'sh e e t s dev elop e d , and pilot plant s run using various carbox ylic acids. 8ussia n inves tig a t o r s ->indin, "#$< a , b/ >indin "#$"/ 0obikov, "#$). pion e e r e d this are a using C C C # fatty acids. 5ater, in the ?F -;letch e r, "#$=, "#$#. a pilot plant 'as run using nap h t h e nic acids, and abou t that time 1srael 'as using the alph a bro m ol a u ric -0lumb e r g , "#$#. extr ac t a n t for the sep ar a tio n of 7i Co. The Shell 4il Comp a n y -Spit&er, "#$$. in %mst er d a m dev elo p e d the tertiary mon o carbox ylic acids 'hich are less soluble in the a,u e o u s phas e as comp a r e d to the previou s naph t h e nic carboxylic acids. The carbox ylic acid rea g e n t s includ e d 6ersatic #, 6ersatic "<, 6ersati #"". Event u ally, 6ersatic "< 'as select e d for mark e tin g. 1n the late "##<Ts, the rea g e n t 'as sold to Cognis. %s not e d earlier, in the acid side the

selectivity is for 7iECo -and the revers e on the alkaline side of extr ac tio n.. Sumito m o 2etal 2ining Comp a n y in Sapan use this rea g e n t , 6ersatic "<, for the co extr ac tio n of 7iHCo from the solution follo'ing a pres s u r e leach of a sulphid e mixe d precipita t e and remo v al of impurities -Suet s u n a , "#D<.. The load e d solven t is stripp e d 'ith stron g +Cl and this strip solution cont a c t e d in a secon d circuit 'ith a tertiary amin e to extr a c t the Co and so sep a r a t e it from the non extr a c t a bl e 7i. The flo'sh e e t is given in ;ig. "3=, and ;ig. "3* sho's the typical extr a c tion curve s for sever al me t al s. 2intek in South %frica hav e describ e d a proc e s s for the recov er y and sep a r a tio n of Co and 7i from a tankho u s e effluen t using the 6ersatic "<, as 'ell as the recov e r y of the soluble orga nic carboxylic rea g e n t loss es -Cole, "##*.. Tertiary !min e s Sever al comp a ni e s , 'her e the leach is in +Cl inste a d of + 3 S4 = , as abov e , use the tertiary amin e s to sep a r a t e Co from the non extr a c t a bl e 7i -Thornhill, "#C"/ !igstol, "#C"/ ;letch e r, "#C)/ %ue, "#C"/ 0o&ec, "#C=.. ;or exa m pl e , in the ;alconbridg e proce s s , ;e is remo v e d by T0P, follo'ed by the amin e extr ac tio n of Co. 1f Cu is pres e n t , then it 'ill co extr ac t. 7i rem ain s in the raffinat e . The Cu and Co are sep a r a t e d by a selective strip, follo'ed by subs e , u e n t purification circuit for Co. %n early description of the refinery is depict e d in ;ig. "3$. 0oth 2etallurgie +oboke n in 0elgiu m -;letch e r, "#C). and Societ e 5e 7ickel in their 5a +avre ;ranc e plant -0o&ec, "#C=. use a chloride leach and amin e s for the sep a r a tio n of Co 7i -;ig "3C, "3D.. E8tra 9 ti o n !ro 7 AlCalin e Me;i u 7 =xim e s The oxime s hav e be e n used in oper a tin g plants , and one of the earlies t 'as that of the SEC Corpor a tio n in Texas. ;ollo'ing the remov al of Cu from an acidic solution, the p+ 'as ad(us t e d to abou t p+ D.*, the Un extr a c t e d , follo'ed by 7i extr a c tion 'ith 51X $=7 -Ellas e n, "#C=. as sho'n in ;ig. "3#. The extr ac tio n of 7i is som e ' h a t similar to that describ e d for 7ippon 2ining earlier. 1n the mor e rece n t Bue e n sl a n d 7ickel proce s s in %ustralia for tre a tin g the am m o ni a c al leach solution, the oxime 51X DC B7 is use d to extr ac t the 7i. The Co is subs e , u e n tl y recov er e d by a seco n d solve n t extr a c tion circuit -8eid, "##).. Extraction curve s for anot h e r oxime, 51X D= are given in ;ig. ")< and ")".

@ersatic #2 The extr a c tion and sep a r a tio n of Co 7i from the Rreduction end solutionR 'as pilote d in Cana d a -8itcey, "#C".. ;ollo'ing an am m o ni a leach of sulphid e s -repr e s e n ti n g the Sherritt proce s s ., Cu 'as extr a c t e d and sep a r a t e d from Co and 7i in the leach solution 'ith 51X $=. 6ersatic "< 'as use d, follo'ing the 7i reduction stag e , to extr ac t Co from the am m o ni u m sulph a t e solution at p+ D.*. This res ult e d in a good sep a r a tio n over 7i -;ig. ")3 ")=. The 7i could be subs e , u e n t l y recov er e d by any of sev er al oxime s , similar to that describ e d abov e . 1E&P! The alkylpho s p h o ric acid can also be use d to sep a r a t e Co 7i from alkaline me diu m . +o'ev er the anionic stre n g t h is critical in the loading efficiency, and so not gre a t e r than abou t =< g 7+ = S4 = E5 can be tolera t e d at p+ "" -8itcey, "#$#.. This extr a c tion curve 'as not e d earlier as ;ig. C in Section 11. )iluents 4ne of the ma(or comp o n e n t s of the solven t mixtur e is the keros e n e diluent. 4ver the ma n y years of the application of solven t extr a c tion to the sep a r a tio n and recov er y of Co 7i ther e has bee n ma n y improv e m e n t s to the type and perfor m a n c e of the diluent. The diluent com m o nl y us ed in %ustralia, Shellsol 3<=$, is a result of res e a r c h and dev elo p m e n t to improv e phas e sep ar a tio n and selectivity, as 'ell as oper a t e at a safe te m p e r a t u r e bec a u s e of the high flash point. 0eca u s e of the solven t mixtur e, including the diluent, and the fact that the extr a c tion proce s s 'ith thes e laterit e s is perfor m e d at abou t *< C, the phas e sep ar a tio n is extr e m e l y rapid. 4f cours e phas e sep a r a tio n dep e n d s on oth er factors than diluen t and te m p e r a t u r e , and thus 'ill be affect e d by the typ e of a,u e o u s feed solution and its comp o sition, such as colloids and solids. This tog e t h e r 'ith the type of agita tio n -she a r. 'ill dicta t e the rate and comple t e n e s s of coales c e n c e , and ther efor e the design of the settlers as 'ell as the solve n t entr ain m e n t loss e s.

A00lication o$ SX to aterite each Sol7tions The succ e s sful application of solven t extr a c tion, to any situ a tion, mus t consid er the natur e of the feed solution, the che mis tr y -met als, impurities, anions, acidity alkalinity, specia tio n. and the physic al che mis tr y -solids, colloids, density differe n c e s bet' e e n solven t and feed, emulsion ten d e n c y and thus she a r that can be tolera t e d . . !heth e r the sourc e mat e ri al is a sulphid e ore or a sulphid e precipita t e , or a laterit e depo sit, the application of solve n t extr a c tion 'ill be similar. The differe n c e 'ill be the appro a c h to the proce s s dev elo p m e n t due to

differe n t typ e s and conce n t r a tio n s of impurities. 4nce the feed mat e ri al, 'het h e r a laterit e or a sulphid e, is leach e d the sep a r a tio n tech ni, u e s 'ill be similar for both solution s. The main differe n c e s are the res p e c tiv e met als conc e n t r a tio n s and the relativ e amo u n t s of impurities . The impurities 'ill re,uir e consid e r a tio n, and prob a bly remo v al, eith er befor e the solven t extr ac tio n of Co and 7i, or selectively remo v e d during the SX proce s s . Thus slightly differe n t principles of solven t extr ac tio n sep ar a tio n tech ni, u e s and che mis tr y may hav e to be use d. +o'ev er, the ma(or impurity in all feed solutions is that of iron. The precipita tio n re mo v al proce s s is similar in all plant s. The proc e s s of sep a r a tio n and recov er y of pure cobalt and nickel produc t s has bee n succ e s sfully applied to both sulphuric acid leach solutions as 'ell as thos e resulting from am m o ni a leach proce s s e s . The com m o n proce s s has bee n that of the sulphuric acid leach rout e. %t pres e n t , ther e is only one plant using the am m o ni a c al extr a c tion syst e m . 5aterite s hav e bee n the sourc e feed. 1n som e of the pres e n t oper a tin g plants , the feed ma t e ri al is a mixe d 7i Co sulphid e precipit a t e from laterit e tre a t m e n t that is dissolve d in sulphuric acid and furth e r refine d by solve n t extr a c tion. %lthoug h the pres e n t gro'th and application s of solven t extr a c tion in %ustralia is rapid, nev er t h el e s s it has bee n slo' comp a r e d to that in som e other countrie s. This is particularly so for copp e r, and cert ainly for nickel and cobalt. +o'ev er, 'ith the pres e n t 'orld inter e s t in 7i and Co ther e has result e d an inten s e inter e s t by %ustralian comp a ni e s in the application of solven t extr ac tio n to recov e r y of thes e met als . 7ickel comp a ni e s aroun d the 'orld that hav e nev er applied solven t extr a c tion to recov er y of Co and 7i no' appr e ci a t e the cost ben efits of using this app a r e n t Rne' tech n olog yR rath e r tha n the muc h older, exp e n siv e tech n ologie s . 1nde e d , ther e are sever al comp a ni e s that hav e claim e d pay off of their "< year amorti& e d solven t extr a c tion oper a tio n in a year. Co*(i Solvent Extraction Process Flo,sheets :uring "###, thre e ne' plants for the recov e r y of 7i from lateritic ors 'ere put on stre a m @ %nacon d a 2urrin 2urrin/ 8esolut e 0ulong/ and Cent a u r Ca's e plant s. Table )< sho' s som e of the %ustralian comp a ni e s pres e n tly dev eloping tech n olo g y for application of solven t extr ac tio n to their ne' or modified oper a tio n s . There are ma n y possible proc e s s flo'sh e e t s that can be consid er e d in the tre a t m e n t of nickel cobalt be aring solution s. The proc e s s 'ill usu ally be dep e n d e n t on@ a. the feed comp o sition 'ith resp e c t to the cobalt and nickel conce n t r a tio n s / b. the impurities/ and c. 'het h e r the leach has bee n 'ith sulphuric acid, hydroc hloric acid, or alkaline am m o ni u m carbo n a t e or am m o ni u m sulph a t e . The flo'sh e e t s 'ill differ in the

philosop h y of sep a r a tio n s , and thus may ce m e n t a t i o n , solven t extr a c tion, or ion exch a n g e .

includ e

precipit a tio n,

1n all the flo'sh e e t s , follo'ing acid pres s u r e leaching, the iron mus t be remo v e d prior to SX, usu ally by neutr ali&ation precipit a tion. This sep a r a tio n ma y be follo'ed by the remo v al of Cu and Un. %lso, 2n ma y be remov e d from the leach solution. 1n ;ig. ")* and ")$ are sho' n som e of the various options, and the similarities and differe n c e s in flo'sh e e t s dep e n di n g upon the ore and solution typ e and the particular ob(ectiv e s of the comp a n y in the typ e of produc t s that are to be produc e d after an initial + 3 S4 = leach. Then the choices begin. :epe n din g upon the extr a c t a n t select e d , and the natur e of the a,u e o u s feed solution as reg ar d s anionic conce n t r a ti o n and p+, the order of extr a c tion as 'ell as impurity re(ection 'ill be det er mi n e d . 4ne proce s s is to tre a t the solution directly for the recov e r y of Co follo'ed by the recov er y of 7i by SX E!. 1n an acidic sulphuric acid leach li,uor, the Co is usu ally extr ac t e d and sep a r a t e d from 7i at abou t an e,uilibriu m p+ ranging from abou t p+ =.* *.*. The 7i can the n be subs e , u e n t l y recov er e d from the slightly acidic raffinat e , or follo'ing neutr ali&a tion to the alkaline p+ and the n extr ac tio n. ;rom an alkaline solution, 7i is prefer e n ti ally extr a c t e d in som e cas e s , 'hile 'ith a differe n t extr ac t a n t Co is extr ac t e d ahe a d of 7i. 1n the cas e 'her e 7i is prefer e n ti ally extr ac t e d to Co, it 'ill prob a bly be due to the fact that the Co is in the trivale n t stat e , the oxidation stat e at 'hich it is not extr a c t e d und e r the conditions re,uire d for 7i extr ac tio n. +o'ev e r in that syst e m -chela ting., unles s all the Co is in the trivalen t stat e , any Co 3H pres e n t 'ill be co extr a c t e d 'ith the 7i and oxidi&e 'hile on the orga nic solution to the Co )H . The trivale n t form is mos t difficult to strip from the solven t, and usu ally re,uire s a reducing strip proc e s s . %ltern a tiv ely, perh a p s a bulk precipita t e of sulphid e, hydroxid e, or carbo n a t e ma y be desire d as a sale a bl e produc t, eve n thou g h the s e produc t s do not gen e r a t e the sa m e reve n u e as a more purified prod uc t. 4r the s e precipita t e s can be consid e r e d as inter m e di a t e to the refining stag e , in 'hich the precipita t e s are re dissolve d in acid or am m o ni a . 7ickel and cobalt are recov e r e d from thes e more conce n t r a t e d li,uors by SX E!. 4ther rout e s hav e includ e d the direct precipit a tion from the leach solution of a mixed hydroxid e for furth e r refining. 0oth the sulphid e and hydroxid e precipit a t e s hav e be e n used as inter m e d i a t e produc t s in a proce s s that 'ould subs e , u e n t l y leach the precipit a t e s , follo'e d by purification by solven t extr a c tion.

Ta l e 306 Som e :eveloping Plants for CoE7i 8ecov er y COM&A"Y C8% 4utoku m p u :ominion %E&OSIT +oneym o o n !ell Aakabindi TY&E 5aterite LEACH Press ur e %cid Press ur e %ctivox Pres s ur e _ 0acteria &ROCES S SX RECO,ER Co, 7i

Sulphid e

SX E!

Co, 7i

Presto n 212

2arlborou g h 2T. 1sa

5aterite Sulphid e Conc. Sulphid e 5aterite

SX_ SX 2ixed S_ SX E! SX E!

Co, 7i Co 7i

212 7ord +ighlan d s >old Bue e n sl a n d 7ickel !est e r n 2ining >oro

2T. 1sa ;lot Tails 8amu 8iver -P7>.

8oast 5each Press ur e %cid

Cu, Co Co, 7i

B75 8efinery !2C 8efinely 17C4

7i 8aff. Solution 2ixed Sulphid e 5aterite

5each Sulphid e Press ur e %cid Press ur e %cid

SX

Co

SX E! SX E!

Co Co, 7i

.e/ection of Impurities !hile the sep a r a tio n and recov e r y of Co and 7i prod uc t s might be consid er e d to be relatively eas y by using solven t extr a c tion, nev er t h el e s s in order to produc e high purity final sale a bl e produc t s ther e are sever al impurities that mus t be consid er e d for re(ection. The re(ection proce s s may involve@ neutr ali&a tio n precipita tion/ oxidation precipita tion/ che mic al precipita tio n/ control of valenc y stat e by redox/ selective scrub bin g stripping/ and strip of produc t plus impurities follo'ed by tre a t m e n t of the strip solution for final purification.

The ma(or cont a mi n a n t s are ;e, Cr, %l, Ca, 2g, 2n. 4ne of the ma(or cont a mi n a n t s is that of iron, and this is usu ally remov e d by oxidation neutr ali&a tio n precipita tion. Temp e r a t u r e , reag e n t type, cont a c t time, and settling mus t be consid er e d to optimi&e the precipita tion as 'ell as to minimi&e the amo u n t of occlud e d me t al value s . 0oth %l and Cr are usu ally remov e d in this stag e of purification. 2ang a n e s e is anot h e r ma(or cont a mi n a n t in laterit e leach solutions , and like iron, usu ally is co extr ac t e d 'ith eith e r the Co or the 7i. This ma y be remo v e d prior to extr a c tion, or dealt 'ith later in the strip li,uor as a purification stag e of the cobalt or nickel electrolyt e. 4xidation precipita tion as 'ell as che mic al precipita tion has bee n use d. Calcium and ma g n e s i u m can be a proble m , dep e n di n g upon the extr a c t a n t select e d for the sep ar a tio n of 7i Co. 1f Ca has be e n re(ect e d bec a u s e of the rea g e n t selection, nev er t h el e s s 2g ma y still be a ma(or cont a mi n a n t . 1f co extr ac t e d 'ith eith er 7i or Co, 2g is a cons u m e r of che mic als use d in the extr a c tion, as 'ell as occup ying extr ac tio n sites other'is e available for eith e r 7i or Co loading. ?sually 2g can be selectiv ely scrub b e d from the solven t. :epe n din g upon the extr ac t a n t select e d , other possible cont a mi n a n t s that can result in proce s s concer n s includ e Cu and Un. 1f the conc e n t r a ti o n s of one or both of thes e cont a mi n a n t s are high, the n perh a p s a sep a r a t e remov al stag e using solve n t extr a c tion ma y be re,uir e d prior to the sep a r a tio n and recov er y of Co and 7i produc t s . 4ther'is e, if in small conc e n t r a tio n s , and again dep e n di n g upon the extr a c t a n t s select e d , the a,u e o u s feed solution, and the oper a tin g conditions , thes e cont a mi n a n t s ma y be remov e d by selective stripping -scrub bin g.. Solvent Extraction Test Program The flo'sh e e t 'ould be bas e d on the tre a t m e n t of 7i be aring solutions resulting from the pres s u r e leaching of laterit e s . The 8 9 : progr a m can be consid e r e d to be divide d into abou t C phas e s . -i. -ii. -iii. -iv. -v. -vi. -vii. 5itera t u r e searc h/ similar oper a tio n s 1nitial tes ts flo'sh e e t possibilities :efinitive tes ts on flo'sh e e t dev elo p m e n t proce s s flo'sh e e t Evaluation of proce s s on mini scale continuo u s Possible furth e r bench tes ts 4ptimi&ation testin g on mini scale continu o u s Small scale continu o u s tes ting -pilot plant.

and

conc e p t u a l

Considerations in )esign 2any asp e c t s hav e to be consid e r e d in the design of the extr a c tion proce s s , and includ e the follo'ing import a n t are a s @ X X X X X Che mis tr y Extracta n t s < )odifiers< 1iluent s 2ass transf er 1ispersion and Coalesc e n c e E,uip m e n t Selection and =peration Econo mics Environ m e n t a l and Solvent s 5osses solve n t

The abov e decisions hav e to be comp a tible 'ith the nat ur e of the feed solution G the che mis tr y -met als, impurities, anions, acidity alkalinity, specia tio n. and the physical che mis tr y -solids, colloids, den sity differe n c e s bet' e e n solve n t and feed, emulsion tend e n c y and thus she a r that can be tolera t e d . . %ll impac t on the possibility of the succ e s sful design, and if som e are partially ignor e d then proble m s in the plant oper a tio n can be anticipa t e d . !heth e r the sourc e ma t e ri al is a sulphid e depo sit or a laterit e depo sit, the application of solve n t extr a c tion 'ill be similar. The differe n c e 'ill be the appro a c h to the proce s s dev elop m e n t due to differe n t typ e s and conc e n t r a ti o n s of impurities . Thus differe n t principles of solve n t extr a c tion sep a r a tio n tech ni, u e s and che mis tr y hav e to be used. Final Products :epe n din g upon comp a n y philosop hi e s and mark e t s , the final produc t s hav e varied in the 7i Co plants . There has, in the pas t, bee n consid e r a bl e produc t s of mixe d sulphid e s prod uc e d and mark e t e d to a refiner, such as Sherritt >ordon, 'ho 'ould produc e cobalt and nickel met al po'd er s and bri,u e t t e s follo'ing hydro g e n reduction of the resp e c tiv e a,u e o u s solutions . 4ther rout e s hav e includ e d the precipita tion of a mixe d hydroxid e for furth e r refining. 0oth the sulphid e and hydroxid e precipit a t e s hav e be e n use d as inter m e di a t e produc t s in an oper a tio n that 'ould subs e , u e n tl y leach the precipita t e s and purify by solven t extr a c tion. !ith the dev elo p m e n t of the solven t extr a c tion sep a r a tio n techn olo g y has be e n the dev elo p m e n t of electro'in nin g of the res p e c tiv e met als from the strip solution s. +ydrog e n reduc tio n could also be applied to such solution s. 0oth proce s s e s , couple d 'ith the solven t extr ac tio n, hav e the cap a bility of producing very high ,uality me t al cobalt and nickel produc t s .

O0eration %lthoug h the choice of the solven t -extr a c t a n t consid er e d as the single mos t import a n t asp e c t in proce s s , ther e are addition al import a n t factors to contribut e to'ard s the ultima t e purity that 'ill includ e the follo'ing@ X X X X X X X X X X feed solution comp o sition diluent selection stag e s scrub solution typ e and conc e n t r a ti o n phas e continuity relativ e kinetics of each me t al disper sion and coales c e n c e te m p e r a t u r e e,uip m e n t selection and oper a tio n control and diluen t. is often the solven t extr a c tion consid e r, all of 'hich be achiev e d . Thes e

Process and En*ineerin* Iss7es .elia&ility of Scale*0p 5ike any unit oper a tio n in hydro m e t a llur g y, the scale up can be extr e m e l y reliable, but for any typ e of scale up to be reliable the nec e s s a r y dat a on che mis tr y and physic al asp e c t s of the proc e s s mus t be und er s t o o d . ;or exa m pl e , in the Eldora d o 2ining design of the original Co 7i sep a r a tio n proc e s s using :E+P% -8itcey, "#$D/ "#C* b., the alkylpho s p h o r u s acid, the benc h and pilot test s 'ere succ e s siv ely scale d up in puls e colum n s , starting 'ith * cm, to "* cm, then to 3* cm and finally to the plant design of ** cm dia m e t e r . The perfor m a n c e on scale up 'as predict e d , and the over all efficiency actu ally improv e d 'ith scale up. 7ormally ther e 'ould not be the re,uire m e n t for so ma n y sta g e s in the scale up proc e s s , but that plant 'as the first, and ther efor e not only 'as the che mic al proc e s s ne', but the application of the puls e colum n s at that time in the mid "#$<^ s 'as also ne'. 4ther plant s that 'ent throu g h the scale up from bench throu g h to pilot plants 'ere 7ippon 2ining 'ith the introdu c tion of the phos p h o nic acid extr a c t a n t and the use of centrifug al cont a c t o r s inste a d of puls e column s -after licensing the abov e phos p h o ric acid proc e s s and applying the tech n olo g y.. 1n the Tocatins plant, 'hich 'as design e d and built by the comp a n y, the proce s s 'as design e d on benc h scale, and the n succe s siv e pilot plant s 'ere run to optimi&e the reag e n t selection and the design of the final plant. %t Sumito m o 2ining, they chos e to go to a 3 stag e extr a c tion syst e m 'her e the Co and 7i 'ould be co extr ac t e d from the acid leach 'ith 6ers atic acid, stripp e d 'ith hydroc hloric acid and the Co subs e , u e n t l y sep a r a t e d from the strip solution 'ith an amin e.

Economics Th e econo mic s of any proce s s select e d 'ill of cours e dep e n d upon the capit al and oper a tin g costs of the proc e s s . ?ntil comp a r a tiv e dat a are available for a given situa tion, any estim a tio n s are of little use. 2any of the plants are often depr e ci a t e d over a "< year period. 7evert h el e s s ther e hav e be e n at leas t a fe' kno'n nickel oper a tio n s that 'ere so succe s sf ul that much less tha n ) years 'as re,uire d. The capit al costs consist of the e,uip m e n t , installation, and the initial solven t fill. The oper a tin g costs includ e the rea g e n t s , solven t pre tre a t m e n t , po' er, solven t loss e s, an alys e s , maint e n a n c e , labour, ad ministr a tio n, and the depr e ci a tion on the capital. The ma(or factors that affect the costs are@ flo' rat e s , feed conce n t r a ti o n, solven t conce n t r a tio n, e,uip m e n t choice, and me t h o d of plant oper a tio n reg ar din g she a r, emulsions and cruds. 4ne of the ma(or cost factors in the plant is the li,uid solids sep a r a tio n and clarification. The application of solven t in pulp extr a c tion could be applied in cert ain cas e s and thus a significan t cost reduc tion to the over all plant 'ould res ult -8itcey, "#C).. 1n addition, reduc e d soluble loss e s to the filter cake 'ould result. %noth e r possible cost reduction in the over all plant or refinery proc e s s 'ould be pres s u r e reduction applied directly to the orga nic pha s e to produc e met al po'd e r s -0urkin, "#$#/ "#C"/ van der Ueeu', "#C3.. 7ot all reag e n t s 'ill 'iths t a n d such a tre a t m e n t , but of thos e rea g e n t s exa mi n e d the :E+P%, 6ersatic "<, and Felex "<< all resist degr a d a tio n . +o'ev er the proc e s s has not gon e beyo n d pilot plant testin g.

Concl7sion There are ma n y options and combin a tio n of proc e s s e s that may be consid er e d in the tre a t m e n t of laterit e or other 7i Co solution s. The selection of the extr a c t a n t should be bas e d on a comp a ris o n of test dat a from sever al possible rea g e n t s on that particular leach solution, for each situa tion is uni,u e. The me t h o d of impurity remov al 'ill be dictat e d by sev er al factors, including the choice of the extr ac t a n t . 8eag e n t loss e s by entr ain m e n t and stable emulsions and cruds mus t be consid er e d and bala nc e d agains t the price of the reag e n t and che mic al perfor m a n c e . ;inally, the selection of the cont a c tin g e,uip m e n t as reg ar d s the physic al oper a tio n and re,uir e d sta g e s should be a consid e r a tio n in the design and optimi&a tion of the proce s s .

Re$erences %ndo, 2., Emoto, S., Takah a s hi, 2., Fasai, T., and 7akaya m a , +., 7ickel and Cobalt 8efinery of 7ippon 2ining Comp a n y. Paper pres e n t e d at Cth %nnual +ydro m e t a llurg y 2eeting, C12, 6ancouv e r, "#CC. %ue, %., Sk(utar e.>., 0(orling., 8einh ar d t , +., 8ydb er g, S., Proc. 1SEC^C", The +agu e, "#C", Pub Soc. Che m 1nd., 5ondon. 0lumb e r g , 8., 2el&er, P., 8ecov er y of Com m o n 0as e 2etals by a Solven t Extraction Proces s , in Proc. 611 1nt. 2in. Proces s Congr e s s , "#$=, 6ol ", pp ")* "=* ->ordo n 9 0reach Pub, 7e' Aork.. 0obikov, P.1., and >indin, 5.2., 1nt, Che m, Eng,. ), 7o. ", ")) )D,"# $ ) . 0o&ec, C., :em a r t h e , S.2., and >ando n, 5., 8ecov er y of 7ickel and Cobalt from 2etallurgic al !ast e s by Solven t Ebion, in Proc. 1ntern a tio n al Solven t Extraction Confer e n c e , 1SEC^C=, 5yon, 6ol. 3, pp "3<" "3)<, " # C = . 0urkin, %.8., Po'der 2etall., "3, pp 3=) 3*<, "#$#. 0urkin, %.8., and 0urge s s , S.E.%., Production of +igh Purity 2etal Po'der s by :irect Pres s ur e 8eduction of 5oade d Extract a n t s , in Proc. of ;irst +ydro m e t a llur g y 2eeting, C12, 4tta' a, 3D 3# 4ctob e r, "#C", pp *" $3. Clem e n t e , :.:.S., :e' ar, 0.1., +ill, S., 2!S Cobalt 8efining 4pera tion South %fricacs ;irst, Paper pres e n t e d at Cobalt^ D <, C12 +ydro m e t a llurg y 2eeting, Edmo n t o n , 3$ 3D 4ctob e r, "#D<., Paper 7o. C. Cole, P.2. and ;eath e r , %.2., % Solven t Extraction Proces s to 8ecov er Copp er and 7ickel from a Tankho u s e Effluent, in Proce e din g s of Copp er # * , Santia g o, Chile, 7ove m b e r "##*/ 6ol ), pp $<C $"$. -C12, 2ontre al. Cook, 5.;., and S&tnok aluk, 8efining of Cobalt and 7ickel Sulph a t e Solutions by Solvent Extraction using di-3 ethylh e x yl. phos p h o ric acid, in Proc. 1ntern a tio n al Solvent Extraction Confer e n c e , 1SEC^C", The +agu e, pp =*" =$3. Eliage n, 8.:., Edmu n d s , E., The S.E.C. 7ickel Proce s s , in C12 0ull., $C@D3 D$, ;eb. "#C=. ;letch e r, %. !. and +est er, F.:., % 7e' %pproac h to Copp er 7ickel 4re Proces sin g, Trans. Soc. of 2ining Engine e r s , %12E, 33#, pp 3D3 3#", "#$=. ;letch e r, %.!. and ;lett, :. S., The Sep ar a tio n of 7ickel from Cobalt by Solven t Extraction 'ith a Carboxylic %cid, Paper pres e n t e d at %nnual %12E me e ti n g, !ashingt o n , ;ebru a r y "#$#.

;letch e r, %.!., Che mis tr y and 1ndus tr y, 2ay "#C), pp ="= ="#. >indin, 5.2., 0obikov, P.1., Fouba, E.;., and 0uga e v a , %.6., 8ussian S. 1norg. Che m., *, 7o. D, pp #<$ #"<, %ug "#$< a . >indin, 5.2., 0obikov, P.1., Fouba, E.;., and 0uga e v a , %.6., :istribution of 2etal Soaps :uring Excha n g e Extraction s , in 8ussian S. 1norg. Che m., *, 7o. "<, pp ""=$ =#, 4ct "#$< b. >indin, 5.2., 0obikov, P.1., Fouba, E.;., and 0uga e v a , %.6., Excha n g e 8eaction of Soap s 'ith Salts of 2ineral %cids, in 8ussian S. 1norg. Che m., $, 7o. "3, pp "="3 "$, :ec "#$". Presto n, S.S., Solvent Extraction of Cobalt and 7ickel 4rga n o p h o s p h o r u s %cids, ". Comp a ris o n of Phoric, Phosp h o nic Phosp hinic %cid Syst e m s , +ydro m e t a llur g y, # -"#D3. pp. ""* ")). by and

8eid, S.>., Price, 2.S., -a. Sep ar a tio n and 8ecov er y of 7ickel and Cobalt in %mmo ni ac al Syst e m s Proces s :evelop m e n t / and -b.%mm o ni a c al Solven t Extraction at Buee n sl a n d 7ickel Proces s 1nstallation and 4per a tio n, in Proc. 1SEC^#), Aork, ?.F. Pub. SC1, "##), pp -a. "*# "$$, -b. 33* 3)". 8itcey, >2., %shbrook, %.!., Sep ar a tio n of Cobalt and 7ickel by 5i,uid 5i,uid Extraction from %cid Solutions, ?.S. Pate n t 7o. ),)# #, < * * -"#$D.. 8itcey, >.2., %shbrook, %.!., Sep ar a tio n of 7ickel and Cobalt in %mmo ni ac al Solutions by 5i,uid 5i,uid Extraction, Trans. 1nst. 2in 9 2etall., C*C C$), Sune "#$#. 8itcey, >2., 5ucas, 0.+., Proce s s for the 8ecov er y of Cobalt from %mmo ni ac al Solutions ?sing a Carboxylic %cid, Proc. 1SEC^C", The +agu e, "# 3) %pril, "#C", 6ol ", pp =$) =C*, Pub Soc, Che m. 1nd. 5ondon. 8itcey, >.2., Slater, 2., 5ucas, 0.+., % Comp a ris o n of the proc e s sin g and Econo mics of ?raniu m 8ecov er y from 5each Slurries by Continuo u s 1on Excha n g e or Solvent Extraction, in Proc. 1nt. +ydro m e t a llur gic al Symp., %12E, Chicago, ;eb. "#C), pp ="# =C=. 8itcey, >.2., Proces sin g of the 0urundi 5aterite s for the 8ecov er y of 7ickel and oth er 6alues, Confiden ti al 8eport prep a r e d for the ?nited 7ations, ?7:P, ;ebru a r y "#C* a . 8itcey, >.2., %shbrook, %. !., and 5ucas, 0.+., :evelop m e n t of a Solven t Extraction Proces s for the Separ a tio n of Cobalt from 7ickel, C12 0ull. $D@ """ "3), San. "#C* b. 8itcey, >.2., and %shbrook, %.!., Solven t Extraction Principles and %pplications to Proces s 2etallurgy, Part 1 and Part ""., Pub. Elsievier Scienc e Publishing Comp a n y, %mster d a m , "#C#, "#D3.

8itcey, >.2., Pres e n t e d in Short Cours e in Perth, 2ay "$, "##$ as part of 7iECo SXEE! Semin a r. Spit&er, E.5.T.2., 8add er, S., 2uys, +. 2., RSelective Extraction of 2etals from %,ueo u s Solutions by Synth e tic Carboxylic %cidsR, Paper pres e n t e d at the XXX6 Congr e s s 1ndus t. Che m., 0russ els, "3 "$ Sept. "#$$. Suet s u n a , %., 4mo, 7., 1to, T., and Aamad a , F., RSumito m o ^ s 7e' Proces s for 7ickel and Cobalt 8ecov er y from Sulfide 2ixtureR, Paper pres e n t e d at 2etallurgic al Society of %12E, ;ebru a r y "#D</ Paper %D< 3, Pub. 2etallurgic al Soc. %12E. %lso pap e r pres e n t e d at Cobalt^ D < +ydro m e t a llur gic al 2eeting, C12, Edmon t o n , 4ctob er "#D<. Thornhill, P.>., !igstol, E., and 6an !eert, >., The ;alconbridg e 2atte 5each proce s s , Sournal 2etals, Suly "#C", pp ") "D. ?4P 2ineral Scienc e s :ivision, 0urundi 2etallurgic al prep a r e d for the ?nited 7ations, ?7:P, "#CD. !igstol, E., and ;roylan d, Proces s e s , pp. C" D", in Proces s e s , %nt'er p, 2ay, >enoot s c h a p 2eta alku n d e , Study, 8eport

F., Solvent Extraction in 7ickel 2etallurgic al Proc. of Solven t Extraction in 2etallurgic al "#C", Pub Technologisch 1nstituu t F. 616, %nt'er p e n .

van der Uee u', %.S., Copp er, 7ickel, Cobalt and 1ron Sep ar a tio n Proces s , in ?.S. Pate n t ),C<", $ * < , 4ct. )", "#C3.

SECTION X

RECO%ERY O# PRECIO!S "ETA S

% proce s s 'as dev elo p e d and pilote d, for the co extr a c tion of Pt and Pd from chloride solution. Selective stripping of Pt 'ith 'ater 'as an effective sep a r a tio n. The extr ac t a n t 'as *W 51X 3$ similar to Felex. H *W isodec a n ol modifier in an aro m a tic diluent, Solves s o "*<. The a,u e o u s leach feed solution cont ain e d approxi m a t e l y =<< pp m Pt, 3< ppm Pd, * gE5 +Cl, plus som e Cu, %u, %g -".. %lthoug h Pt extr ac tio n 'as compl e t e in )< seco n d s , Pd 'as not comple t e until abou t 3.* minut e s . 0y pre e,uilibration of the solven t 'ith +Cl the phas e sep a r a tio n rate 'as improv e d . 1n ;igure ")C are given the results of succ e s siv e cont a c t s of the solven t 'ith feed solution. !hile Pt arrived at a maxi m u m , Pd continu e d to load, replacing any co extr a c t e d impurities. 1ncre a s e d te m p e r a t u r e to =* < C, altho u g h improving the phas e disen g a g e m e n t rat e, res ult e d in a lo'er Pt loading -and ther efor e re,uiring mor e stag e s . comp a r e d to ambi e n t te m p e r a t u r e -;igure ")D. The sche m a ti c flo'sh e e t is sho' n in ;igure ")#.. 1n anot h e r proce s s , 51X 3$ 'as use d to co extr a c t PtEPdE%u from a %u refinery li,uor -3.. 1t 'as found that this syst e m had muc h improv e d perfor m a n c e -eg. kinetics. over alkylsulphid e s and oxime s , 'hich hav e also bee n use d in som e refinerie s. The syst e m had excelle n t pha s e sep a r a tio n. The distribu tion coefficient s are sho'n in ;igure "=< for extr a c tion 'ith *<W 51X 3$ H *W isodec a n ol in Solves s o "*< diluen t, as a function of e,uilibriu m +Cl conce n t r a tio n at 3< < C. 1n ;igure "=" are sho' n the distribu tion coefficient s of %u, Pt, Pd as a function of 51X 3$ conc e n t r a ti o n 'ith e,u al conc e n t r a ti o n of isodec a n ol in Solves s o "*<. %u is highly selective in extr a c tion comp a r e d to Pt and Pd 'hich incre a s e in extr a c tion as the solve n t conc e n t r a ti o n 'as incre a s e d . %u loading is high at <."3 2 %u E *W 51X 3$. Extraction isoth e r m s , are given in ;igure "=3. %u is recov e r e d directly by hydrolytic stripping -$< #< < C, 'ith 'at er. for " 3 hours. Pt is stripp e d 'ith 'at er -p+ ".* 3.<. follo'ed by Pd stripping 'ith $ D7 +Cl. The propo s e d flo'sh e e t is sho'n in ;igure "=).

(i5ur e $3 . @ Effect of Succe s siv e Contac t s on Extraction of Pt and Pd

(i5ur e $3 8 @ Effect of Temp e r a t u r e on E,uilibriu m Extraction 1soth er m

(i5ur e $3 9 6 Propos e d ;lo'sh e e t for ;urth er tes ting

(i5ur e $* 0 @ :istribution coefficient s of %u, Pt, Pd in 51X 3$ as a function of +Cl conce n t r a tio n -3< < C/ ) min.

(i5ur e $* $ @ Plots of : %u-111. , : Pt-16. , and : Pd-11. vers u s initial 51X 3$ conc e n t r a ti o n -3< < C/ ) min.

(i5ur e $* 2 @ Extraction 1soth e r m s for Pt-16. and Pd-11. at ).< and $.<7 +Cl conc e n t r a ti o n s -3< < C/ ) min.

(i5ur e -2 36 The integr a t e d circuit for the sep a r a tio n of %u-111., Pt-16., and Pd-11. 'ith 51X 3$ isodec a n ol Solves s o "*< syst e m

Re! e r e n 9 e s 2olnar, 8., Prud^ ho m m e , P.S., 8itcey, >.2., !ong, E.!., C%72ET 8EP48T, 2S5 DC "<-C8., "#DC. :emo p o ulo s, >.P., Pouskouleli, >., 8itcey, >.2., % 7ovel Extraction Syst e m for the 8efining of Precious 2etals/ Pres e n t e d at 1SEC^D$, 2unich, "#D$/ in Proce e di n g s of 1SEC^D$.

SECTION XI

SEPARATION O# >IRCONI!" AND HA#NI!"

HNO:T-P S6stem The proc e s s of extr ac tin g &irconiu m from nitric acid solutions and at the sa m e time sep a r a ti n g the &irconiu m from hafniu m has be e n kno'n for sev er al year s, but until rece n tly no plant has succe s sf ully oper a t e d this proce s s . The main reas o n for the unsucc e s s f ul oper a tio n 'as the pres e n c e of silica gel in the feed solution to the solve n t extr ac tio n oper a tio n -",3.. :uring extr a c tion, the agita tion of the t'o pha s e s caus e d gels to form, making the proc e s s inoper a tiv e. +o'ev er, a succe s sf ul proce s s 'as dev elop e d by Eldora d o 7uclear -),=. using sieve plat e puls e colum n s 'hich continu o u sly handle d the silica cont ainin g feed solution. Eldorad o 7uclear installe d the proce s s at their Port +ope 8efinery, but the plant 'as eve n t u ally shut do'n beca u s e of lack of de m a n d for &irconiu m. The feed mat e ri al to the circuit is &ircon san d, cont ainin g abou t 3W hafniu m on a &irconiu m basis. The san d is he a t e d in the pres e n c e of caus tic to C*< < C, and the res ult a n t cake or frit is then 'at er 'as h e d to remo v e sodiu m silicat e, and finally dissolve d in "37 +7< ) to yield a solution cont aining abou t "<<g UrE5 at a free acid conce n t r a tio n of abou t C.*7. This solution is then sent to the solven t extr a c tion circuit. % sch e m a ti c dra'ing of the pilot plant circuit is sho' n in ;igure "==. %lthoug h pulse column s 'ere effective, 2ixco column s 'ere installed in the plant. The effect of total acidity in the syst e m , on the extr ac tio n and sep a r a tio n of &irconiu m from hafniu m is sho'n in ;igure "=*.

"I-<:HCl S6stem %noth e r proce s s 'as dev elop e d and plants built in the ?.S. for the prefer e n ti al extr a c tion of hafniu m and sep a r a tio n from &irconiu m from hydrochloric acid solutions . This proce s s 'as dev elo p e d at 4ak 8idge and pilote d by the ?.S. 0ure a u of 2ines. The hafniu m 'as extr a c t e d prefer e n ti ally as hafniu m thiocya n a t e from an a,u e o u s mixtur e of hafnyl and &irconyl thiocya n a t e s in +Cl by hexo n e -met h yl isobut yl keton e .. %merica n 2etal Climax, Teledyn e , !ah Chan g and ?gine, 'ho supply clos e to "<<W of the free 'orld &irconiu m, use this proc e s s . The flo'sh e e t , utilising ope n spra y colu mn s , is sho' n in ;igure "=$ -*,$.. ;eed to the extr a c tion colum n s consist e d of an a,u e o u s acid chloride solution cont ainin g &irconiu m and hafniu m, pres e n t as thiocya n a t e comple x e s .

(i5ur e -3 * @ Sep ar a tio n of &irconiu m and hafniu m in nitric acid solutions

(i5ur e $* ) @ Effect of total acidity on extr ac tio n and sep a r a tio n of &irconiu m and hafniu m

(i5ur e -* @ Sep ar a tio n and recov er y of hafniu m and &irconiu m from chloride solutions

Re$erences Feller, !.+., and Uonis, 1.S., Che m. Eng. ;rog., Symp o siu m Series, 6ol. 3C, pp. "<C ""3 -"#* #.. Cox, 8.P., Peter s o n, +.C., and 0eyer, >,+., 1nd. and Eng. Che m., *<, pp. "=" "=), "#*D. 8itcey, >.2., and Conn, F., 5i,uid 5i,uid Separ a tio n of Uirconiu m and +afniu m, Eldora d o 7uclear 5td., 4tta' a , "#$C, 8 9 : 8eport T$C C, Craige n, !.S.S., Soe, E.>., and 8itcey, >.2., Can. 2et. Buart e rly, C.1.2,2., #, -)., pp. =D* =#3, "#C<. Engine e rin g and 2ining Sournal, "$", -"., pp. CD C#, "#$<. >uccion e, E., Che mic al Engine e rin g, ;eb. "#$), pp. "3D ")<.

SECTION XII EN%IRON"ENTA ASPECTS

Introd7ction The constr ain t s 'hich are being impos e d on met allurgic al oper a tio n s in resp e c t to the environ m e n t and 'orker hygien e , are having a subs t a n ti al influenc e on the various proc e s s e s 'hich are being studie d and dev elo p e d for future use. The unit proc e s s e s for solven t extr ac tio n can be no exce p tio n. 1t is ther efor e vital that sufficient be kno'n abou t the effects of a solven t extr ac tio n proc e s s in ter m s of its environ m e n t a l and hygien e impac t s before the proce s s gets to the cons tr u c tion stag e . The purpos e of this section is to bring the s e mat t e r s to the read e r sT att e n tio n, and to indicat e , albeit briefly som e of the proble m s , and 'hat 'e kno' abou t the effect s, of SX proc e s s e s from an ecologic al point of vie'.

H6drocar?ons Petroleu m hydroc a r b o n s are bio degr a d e d to form C4 3 / sev er al factors may limit the rat e of bio degr a d a ti o n , 'hich are as follo's@ orga nis m availability nutrien t availability oxyg e n refract or y nat ur e of som e petrole u m fraction s to bio degr a d a tio n te m p e r a t u r e -lo' te m p e r a t u r e slo's the rate. ecologic al effects

The hydroc a r b o n s consid e r e d here, and 'hich are com m o n in solven t extr a c tion proc e s sin g, cont ain@ norm al paraffins, branc h e d chain par affins, cyclop a r affins -nap h t h e n e s . , aro m a tics , and olefinic hydroc a r b o n s . The degr a d a tio n of a hydroc a r b o n can occur throu g h oxidation to simpler comp o u n d s , eith er directly by expo s u r e to oxyg e n -autoo xid a tio n., or throu g h met a b olis m by micro orga nis m s -microbioloxid a tio n.. %ir oxidation of paraffins, olefins, and ma n y aro m a tics proc e e d s by a free radical chain reaction 'hich is initiat e d by sunlight. 0io degr a d a tio n is exp e c t e d to remo v e rapidly tha n oth er cons titu e n t s . the aliph a tic fraction mor e

1n Table )" are tab ul a t e d sever al orga nic comp o u n d s accordin g to their eas e of bio degr a d a bility. 0io degr a d a b ility of orga nic comp o u n d s such as oils can be enh a n c e d by the pres e n c e of bact e ri a 'hich eat the oil and relat e d hydroc a r b o n s , bre a kin g the m do'n into innocuo u s mat e ri als. Som e practical consid e r a tio n s in the use of bact e ri a are@ bio degr a d a tio n of oil re,uir e s the pres e n c e of bact e ria, nutrien t s , oxyg e n , and 'ater, all at the sa m e time and in the prop e r proportion s . eve n if the prop er nutrie n t s are supplied, all of the nec e s s a r y ele m e n t s 'ill be found tog e t h e r only at the interfac e bet' e e n oil and 'at er. if the oxyg e n used in the deco m p o s itio n com e s from the dissolve d oxyg e n in the 'at er, the reduction in oxyg e n available to marin e life may be mor e da m a gi n g tha n the original spill. Ta l e 3$6 0io degr a d a b ility of Some 4rganics Easil: /io; e 5 r a ; a le n prop a n ol Etha n ol 0en&oic acid 0en&ald e h yd e Ethylac e t a t e Si5 n i!i 9 a n t l : le s s /io; e 5 r a ; a l e Ethlye n e glycol 1soprop a n ol o cres ol :iethyle n e glycol Pyridine trieth a n ol a mi n e ,er: Re s i s t a n t to /io; e 5 r e ; a t i o n %nailine 2etha n ol 2onoe t h a n ol a mi ne 2ethyle t h ylk e t o ne %ceton e

Toxicit6 o$ Some Rea*ents to #ish This has brou g h t us to the obvious fact that solve n t extr a c tion oper a tio n s do hav e solven t loss e s, and that in mos t cas e s thes e loss e s are being disch ar g e d to the environ m e n t . Cons e , u e n tl y the toxicity of solve n t extr a c tion rea g e n t s to a,u a tic life the n beco m e s import a n t . Thus in order to dev elo p prop er 'at er ,uality criteria for the s e reag e n t s 'e mus t det er mi n e their toxicity to' ar d s fish, as 'ell as their bio degr a d a b ility in the environ m e n t . 1n the evalu a tion of toxicity to fish due to che mic als, four fish type s are gen e r ally use d@ fath e a d minno' s , blue gill, gold fish, and guppie s . Table )3 sho' s T5m #$ tes ts at 3* < C for som e orga nic comp o u n d s 'hen test e d on thes e fish. >ener ally the toxicity 'as gre a t e r 'ith soft 'at er, and "<< per cent survival occurr e d at abou t half the T5m value.

The significanc e of the acut e toxicity dat a pres e n t e d here can only be det er mi n e d throu g h a clear und er s t a n d i n g of the conditions und e r 'hich the comp o u n d s test e d are nor m ally use d. This 'ill includ e a kno'led g e of the dos a g e rate s , tre a t m e n t , fre,u e n ci e s , residu al conc e n t r a ti o n in the effluen t, and the comp o sition of the local fish popula tio n. 0eca u s e the res ults 'ere derive d from short ter m toxicity inves tig a tio n s , all value s should be vie' e d as relativ e toxicities only, and should not be use d to ass e s s pote n ti al impact und e r actu al plant conditions. 2uch mor e study is re,uire d before the impac t of solve n t extr ac tio n rea g e n t s on a,u a tic -and other. life can be prop e rly ass e s s e d . Ta l e 32 @ 2edian Tolera nc e 5imits for som e Petroch e mi c al s TL7 9- , /lu e 5 ill s 33.=# 3=.<< "<.<< =3.)) 3<.CD )=.C3 )3.<< =3.*= )"".< 3).DD 3$.<* 3=.<< 7 5 #L -$ +ol;!i s < )=.=3 *".$3 "3.)C 3<.DC 3).3* =3.)) *=.== "D<.< 3)3.3 ==.=# $=.C= *C.$D

Co7 > o u n ; 0en&e n e Chlorob e n & e n e < chlorop h e n ol ) chloropro p e n e < cres ol Cycloh ex a n e Ethylb e n & e n e 1soprop e n e 2ethylacryla t e Phenol Styre n e Toluen e

(at< e a ; s )).=C 3#."3 "".$) "#.CD "3.** )3.C" =D.*" D$.*" "*#." )=.3C =$.=" )=.3C

+u> >i e s )$.$< =*.*) 3<."C *".<D "D.D* *C.$D #C."< 3=<.< )$D." )#."# C=.D) *#.)<

Tables )), )=, )* 9 )$ sho's som e acut e doxicity tes ts for select e d extr a c t a n t s , diluen t s and modifiers.

Ta l e 33 @ %cute Toxicity Static 0ioas s a ys on Extract a n t s and 2odifiers -T5m #$hr. TL7 ?>> 7 @ +u> >i e Minn o D s s %li,uat ))$ <."D Prime n e S2T <.C< Felex "3< "."< =.< ".$ %lamin e ))$ "<.< =.< Rea 5 e n t

1sodec a n ol 51X $=7 T0P 51X C< 6ersatic #"" :3E+P% #$ hr. %ilu e n t 4il 0ase 5ivestock Spray 7apole u m =C< 2entor 3# :X )$=" 1sopar 5 Shell "=< 7S "== Solves s o "*< 1sopar E

"3.< "*.< "D.< )3.< "<3.* "C).<

D.= 3.C #.$ "*.<

Ta l e 2* @ %cute Toxicity Static 0ioas s a ys on :iluent s -T5m

E!!e 9 t 7on toxic 7on toxic 7on toxic 7on toxic 7on toxic 7on toxic Total mort ality 2inno's T5m >uppies T5m T5m

Con9 e n t r a t i o n ?>> 7 @ "<<< "<<< "<<< "<<< "<<< "<<< "<<< "<.C "=.C "<.<

Ta l e 3) @ %cute Toxicity of 8eag e n t s to 8ainbo' Trout and 8ats/ T5m #$hr static test s -mg.5 " . Rea 5 e n t Rain o D Trou t <.*< <.C* ".= 3.= L <.* -est.V 3<V C.* "< <."D <.)3 "".* ").* =# *$ 3D )3 "< L * <V )3 )C Rat s ?intr a > e r i t o neal inGe 9 t i o n @ Y*< *<< "<<< *< "<< L*<<< "<<< *<<< *<< "<<< *< "<< *<< "<<< Y*<< "<< *<< *<< "<<<

Pimen e S2T %mberlite 5% " %doge n 3D) %doge n )D) %lamine ))$ %li,uat ))$ T0P :3E+P% 6ersatic "< :77S% keros e n e . 51X $=7 keros e n e . 3 Ethylh ex a n ol

-in -in

Vnot possible to det e r mi n e due to lo' + 3 4 solubility 74TE@ :ue to lo' solubilities of rea g e n t s in + 3 <, leth al conc e n t r a ti o n s 'ere difficult to att ain. -;orm a tio n of emulsion s could possibly provide bett e r dat a..

Ta l e 3- @ %cute Toxicity to Uebrafish LC)0 ?7 5 #L -$ @ *8 < 9- < <.=# 3.=* L *. $ L C. * L ). 3 <."<D "".= L*$ <.=C "."3 L *.$ L C.* L ).3 <.<#= "".= L*$

Rea 5 e n t Prime n e S2 T %mberlite 5% " %doge n 3D) %doge n )D) %lamin e ))$ %li,uat ))$ T0P :3E+P%

2* < <.=# *.") L *.$ L C.* L ).3 <.")" "".= L*$

$* * < <.=3 "."3 L *. $ L C. * L ). 3 7: "".= L*$

!ater hard n e s s @ "<< m g .5 " as CaC4 ) / p+ C.) D.*/ T I 3* < C/ * fish -Y <. 3 * g each. L me a n s that 5C*< 'as abov e highe s t toxica n t conce n t r a tio n tes t e d 7:@ not det er mi n e d

SECTIO" 'III ECONO"ICS

%lthoug h, in the final analys e s , the econo mics are gover n e d by the capit al and oper a tin g costs of the oper a tin g plant, nev er t h el e s s this econ o mic asp e c t is really det er mi n e d long before the actu al plant has bee n constru c t e d . % nu mb e r of typical factors in the ultima t e econo mic s of the oper a tio n includ e the follo'ing, 'hich go back to the Proces s :esign E Engine e rin g E Constr uc tio n@ X :esign of the me t allurgic al flo'sh e e t Che mis tr y of the feed solution Choice of the solven t syst e m -E,uilibria, kinetics, physical perfor m a n c e . Selection of the cont a c tin g e,uip m e n t X X X X X Succes sful pilot plant cam p ai g n s Prelimin ar y engin e e rin g during pilot trials Continu al revision as econ o mic s dicta t e flo'sh e e t chan g e s :etailed engin e e rin g -including optimu m plant control as 'ell as produc t ,uality control. Constr uc tio n -mat e ri als, 'elding, and maint e n a n c e that can be incorpor a t e d . amo u n t of reduc e d

C%P1T%5 C4STS X X X X X Type and si&e of the e,uip m e n t 1nstallation 0uilding may be re,uired to house process Solvent fill and inventory 2aterials of construction

X X

%utomation and control %nalyses and type -on line, off line.

X +a&ards and safety 4PE8%T17> C4STS X X X X X X X X X X X X Prep ar a tio n of the feed Pretr e a t m e n t of the solven t Scrubbin g of impurities Stripping costs can vary -syst e m 9 plant. Solven t loss e s 8eag e n t s 5abour 9 2ainte n a n c e 5osses of the product in the reffinate Electrical %nalyses :epreciation on capital %dministration

4T+E8 ;%CT48S@ X X X X X X X X X Solvent concentration ;eed concentration ;lo' rates 6iscosity Phase continuity 7umber of stages ;lo' ratio E,uipment choice 2ethod of operation -she a r, emulsion s, crud.

SECTION XI% # O@SHEETS O# THE #!T!RE

There are a nu mb e r of possibilities 'her e small chan g e s in the solven t extr a c tion proc e s s flo'sh e e t can provid e significant econo mic ben efits to the mill oper a tio n. Thes e includ e the follo'ing@ Syner gis t s G ;igure "=C Extract a n t Choice -kinetics and scrub bin g vs "=D Press ur e 8eduction of 4rganics G ;igure "=# Stripping +ydrolysis Precipit a tion G ;igure "*< +ydrolytic Stripping -pres s u r e . G ;igure "*" S1P Press ur e 8eduction or +ydrolytic Stripping Solven t 5eaching Press ur e 8eduction and ;igure "*) ? S1P Strip +ydrolysis and Solution 8ecycle G

selectivity. G ;igure

G ;igure "*3 Solution 8ecycle ;igure "*=

(i5ur e -) @ Comp a ris o n of Proce s s Step s ?sing Syner gis tic Extract a n t s

(i5ur e -- @ Extract a n t Choice and Circuit Si&e.

(i5ur e -. @ Sche m a tic ;lo'sh e e t 1ncorpor a ti n g Press ur e Stripping Precipit a tion.

(i5ur e $) 0 @ Stripping Precipit a tion Circuits 2odification

(i5ur e -8 @ Conce p t u al ;lo'sh e e t for +ydrolytic Stripping Precipita tio n

(i5ur e -9 2 @ ;utur e ;lo'sh e e t 1ncorpor a tin g S1P and Press ur e 8eduction or +ydrolytic Stripping and Solution 8ecycle

(i5ur e $) 3 @ ;uture ;lo'sh e e t 1ncorpor a ti n g Solven t 5eaching, Press ur e 8eduction and Solution 8ecycle

(i5ur e $) * @ ;utur e ?raniu m ;lo'sh e e t 1ncorpor a ti n g S1P, Strip +ydrolysis and Solution 8ecycle. Re! e r e n 9 e s 8itcey, >.2. RSolven t Extraction Pro(ection s to the ;utureR Sep ar a tio n Scienc e and Technolog y, "D-"= 9 "*., pp. "$"C "$=$, "#D). 0urkin, %.8., 0ritish Pate n t ",3"*, * C $ / "#C<. 6an der Ueeu', %.S., 0ritish Pate n t ",3$C, * D $ / 2arch "#C3. !ar'ick, C.C.1., 0ritish Pate n t ",)$ D, # * $ / 4ctob e r "#C=. :emo p o ulo s, >.P., R:irect Copp er Production from a 5oade d Chelatin g Extract a n t -%n %lkylat e d D +ydroxy, uin oline. by Pres s ur e +ydrog e n StrippingR, Thesis, 2c>ill ?niversity, :ept. of 2ining and 2etallurgic al Engine e rin g, 2ontre al/ 7ove m b e r "#D". :emo p o ulo s, >.P. and :istin, P.%., i)YProc e e di n g s of 1ntern a tio n al Solven t Extraction Confer e n c e 1SEC ^D<, 6ol. 3, 5iYg e, 0elgiu m, Paper 7o. D< C$. :emo p o ulo s, >.P. and :istin, P.%., R% Study of the +ydrog e n a tio n of Felex "<< 5oad e d 'ith CopperR/ 1n Press, S, Che m. Techn. and 0iotech n olo g y. :emo p o ulo s, >.P. and :istin, P.%., R:irect Copp er Precipita tio n from a 5oade d Chelating Extract a n t by Pres s ur e +ydrog e n StrippingR/ Sub mit t e d for publication in 2etall. Trans. 0. 5i, 8.X., :emo p o ulo s, >.P. and :istin, P.%., R7ickel 8ecov er y from 5oade d Felex Y " < < by Precipita tio n ?sing +ydrog e n R/ Paper pres e n t e d at the 3"st C12 %nnual Confer e n c e of 2etallurgist s, Toronto, 4ntario/ -%ug. 3# to Sept. ", "#D3.. Stubin a, 7.2. and :istin, P.%., R:irect Cobalt 8ecov er y from 5oad e d Felex "<< by 8eaction 'ith +ydrog e n R, pap e r pres e n t e d at the 3"st C12 %nnual Confer e n c e of 2etallurgist s, Toronto, 4ntario/ -%ug. 3# to Sept. ", "#D3.. Thors e n, >. and 2onhe mio u s , %.S., RPrecipit a tion of 2etal 4xides from 5oade d Carboxylic %cid Extract a n t s by +ydrolytic Stripping pap e r pres e n t e d at <Dth %12E %nnual 2eeting, ;eb. "#C#, Paper %C# "3. 2onhe mi u s , %.S. and Thors e n , >., in A5oce Y n g s of 1dnterlation al Proce e d s of Solven t Extraction Confer e n c e 1SEC D<, 5iege, 0elgiu m/ Sept e m b e r "#D<, Paper D< #". 8itcey, >.2., Slater, 2.S. and 5ucas, 0.+., in Proce e din g s Svmp o siu m in +ydro m e t a llur g y, Pub. %12E@ pp. ="# =C)/ "#C).

SECTION X%

SX PROCESSIN. P ANTS : PRO- E"S, ASSESS"ENTS, SO !TIONS

Solven t extr a c tion plant s should be rea s o n a bl y trouble free, for the proce s s has -or should hav e. bee n design e d on the basis of soun d che mis tr y/ rea g e n t s selection/ mas s transf er char a c t e ris tics relativ e to the kinetics, e,uilibriu m, stag e s / the influenc e of the continu o u s phas e and the influenc e of the amo u n t and type of she a r re,uire d for mas s transf er/ possibility for the forma tio n of stable emulsions , precipita t e s , and cruds/ selection of the appro pria t e cont a c t o r for the proc e s s , and its prop e r oper a tio n/ auto m a t i o n and control/ and the engin e e ri n g scale up. +o'ev er, it is rath e r surprising that, after almo s t *< years of com m e r ci al solven t extr a c tion plant s that the abov e fund a m e n t a l criteria for design are, to a large ext e n t , ignor e d. The result has be e n that almos t 'ithout exce p tion ther e are proble m s in the solven t extr a c tion oper a tio n s . Thes e Rproble m s R are often not und e r s t o o d , for the plant oper a t o r s recog ni&e that som e t hin g is not perfor min g to design and so the Rsymp t o m R is tre a t e d and not the caus e . The proble m s or Rsymp t o m s R note d by the oper a t o r s includ e the follo'ing@ X X X X X X lo' solven t loading poor ,uality produc t -loading to sat, scrub, selectiv e scrub, 'rong extr a c t a n t , co extr ac tio n vs selective extr ac tio n degr a d a tio n of solve n t -in proce s s and in Cu tankh o u s e . cruds and emulsions precipita t e s exce s siv e solids in the feed -reduc tio n to less tha n 3< pp m.

4f cours e the abov e hav e be e n the caus e of high oper a tin g costs in the sev er al plants bec a u s e the sourc e of the proble m has not be e n det er mi n e d , nor correc tiv e actions take n. 1nste a d , very exp e n siv e ancillary proce s s e s andEor e,uip m e n t are employe d to Rreduc e the impact on the proce s s econo micsR. There are ma n y asp e c t s to be consid e r e d in the design of the solven t extr a c tion proce s s , and includ e the follo'ing import a n t are a s @ X X X X X Che mis tr y Extracta n t s < )odifiers< 1iluent s 2ass transf er 1ispersion and Coalesc e n c e E,uip m e n t Selection and =peration Econo mics Environ m e n t a l and Solvent s 5osses

%ll impac t on the possibility of the succ e s sful design, and if som e are partially ignor e d then proble m s in the plant oper a tio n can be anticip a t e d . The RkeyR in all situ a tion s is to first det er mi n e , logically, the possible caus e of the Rproble m R by@

X X X X X X X

char a c t e ri&ing the Rproble mR by various analys e s verifying Rsusp e c t e d caus eR in benc h test s subs e , u e n t testin g on a continu o u s circuit det er mi nin g possible solution s to the proble m in benc h test s testin g options in a continu o u s circuit evalu a tio n of the relativ e econo mics of the tre a t m e n t proce d u r e s selection of the bes t option and application to the plant

Some Pro?lems D7e to Silica X X X X X X The pres e n c e of Si can caus e or enh a n c e the forma tio n of cruds and emulsions . 2ost cruds are comp o s e d of Si as the ma(or constitu e n t , toge t h e r 'ith ;e 2g Ca %l and the met al being extr ac t e d . eg Cu ?nless ther e is a scrub stag e bet' e e n extr a c tion and stripping, Si and other impurities may carry over and app e a r in the strip produc t. 4rga nic continu o u s oper a tio n app e a r s to minimi&e emulsion form a tion in the pres e n c e of Si. The pres e n c e of humic acids tog e t h e r 'ith Si enh a n c e s emulsion s and cruds, as does high she a r. Solutions cont aining colloidal silica, in the a,u e o u s continuo u s syst e m , are sev er ely ret ar d e d in pha s e sep a r a tio n rat e s and ten d to form stable emulsions . 7oticed in amin e s , alkylpho s p h a t e s and oxime s syst e m s . Colloidal silica and lo' molecular 'eight amin e s result in slo'er phas e disen g a g e m e n t than high er molecular 'eight amin e s . 2ost emulsion s are produc e d by a third phas e emulsifier cons ulting of a colloidal subs t a n c e -such as silica alu min a, hydros ols or clays, ferric or alu minu m hydroxid e or colloidal phos p h a t e . . Each emulsion or crud has its o'n char a c t e ris tics and re,uir e labor a t o r y identification. 2ethod s of identification includ e microsco pic, X ray diffraction, infrare d and emission spectro gr a p hic tech ni, u e s . T0P emulsion s ate stabili&ed by silicic acid. Temp e r a t u r e , acidity and natur e of the a,u e o u s pha s e hav e consid er a bl e influenc e on the stability of the T0P emulsion in the pres e n c e of silicic acid.

X X

X X

Possible met h o d s of prev e n tio n includ e@ o o o o o chan g e s in p+/ addition of flocculating age n t s to remo v e the emulsifier/ addition of disper sio n age n t s to disper s e the emulsifying pha s e / chan g e plant practice to avoid form a tion of the surfac e active mat e ri als/ addition of fluoride or oth er comple x to solubilise the silica colloid.

Ph6sical As0ects A Em7lsion = Cr7ds SX proce s s G proce s s of disper sion of 3 dissimilar solutions and sep a r a tio n by coales c e n c e . The time for mas s tran sf e r to occur 'ill dep e n d on the che mic al kinetics and interfacial conditions . The amo u n t of agita tion, the time of mixing and the pha s e continuity 'ill result in the type and sta bility of the emulsions that are form e d . ?p to a point, the smaller the drop the fast er the rat e of ma s s transf er. +o'ev er 'ith incre a s e d mixing und er high she a r, fine droplet s are produc e d , resulting in incre a sin g difficulty in pha s e sep a r a tio n, as the syst e m appro a c h e s as are a of sta bl e emulsion form a tion. The pres e n c e of surfact a n t s 'ill influenc e coales c e n c e , and und e r high she a r conditions can produc e stable emulsions . %t high she a r rate s and the pres e n c e of air, s regim e of insta bility is produc e d in the pres e n c e of various cations in solution so that the res ult can be the form a tio n of crud. This crud is furth er pro mo t e d in the pres e n c e of solid particles in the circuit, such as dust, ore finesEslim e s , or precipita t e s forme d und er the conditions . Some Factors Causing Crud ". X X X X X X X 7atur e of feed comp o sition cations -;e, Si, Ca, 2g, %l. colloids -Si, %l. solids -dust, ore fines, slimes . anionic hydrolys a bl e specie s -6, ?, 2o, Ur, Si, etc.. bact e ria, fungu s orga nic acids -hu m u c, fulvic. lignin

surfact a n t s

3. 7atur e of Solven t X X X X X possible lack of modifier insufficient aro m a tic cont e n t in diluent `poison e d a solven t unre a c t e d che mic als of rea g e n t ma n uf a c t u r e degr a d a tio n of the solven t -te m p , oxidation, bio..

). E,uip m e n t Selection X X X affects physical char a c t e ris tics no univers al cont a c t o r -ma y re,uir e mor e than a single designEt yp e . consid er in selection@ feed comp, kinetics, and phy che m variable s that affect emulsion forma tio n and ma s s transf er

=. 2ethod 4f 4per a tion +aving select e d the cont a c t o r, att e n tio n and control of@ X she a r conditions X phas e continuity X mat e ri als -'etting char a c t e ris tics. X minimi&e air entr ain m e n t X minimi&eEco n t r ol@ surfact a n t s , bact e ri a, orga nic acids

"ethodolo*6 o$ Cr7d Prevention Evaluation of factors causin g crud. ". 3. Che mic al 9 Physical Char ac t e ri& a tio n che mic al analys e s miner alo g y crud bre aking mec h a ni s m of crud form a tio n 0ench Scale Crud Prev e n tio n Tests she a r -decr e a s e . cont a c t o r typ e -modifyEch a n g e . surfact a n t s -re mo v e . solids -re m o v e . pha s e continuity -org a nic. bact e ri a, fungus -aro m a tic cont e n t . te m p e r a t u r e -incre a s e _ .

scrub bin g -clea n load e d solve n t of impurities. blee d tre a t m e n t of solve n t -re mo v e poison s, degr a d a ti o n prod uc t s .

=. 6erification on Continuo u s Circuit