MQ 55025

SEPARATION OF IRON(II1) FROM ZINC SULPHATESULPHURIC ACID SOLUTIONS USING
ORGANOPHOSPHORIC ACID EXTRACTANTS
Frank T. Principe
Department of Mining and Metaiiurgical Engineering McGI University, Montreai

Apri11999
A Thesis submitted to the
Faculty of Graduate Stiidies and Research

in partial fulfillment of the requirements of the degree of
Master of Engineering
@Frank T. Principe, 1999
s+l
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The author retains ownership of the copyright in ths thesis. Neither the thesis nor substantial extracts fiom it may be printed or otherwise reproduced without the author's permission.
To dear Dawn and our

wonderfui childen
ABSTRACT
I r o n o solvent extraction removal fiom zinc process solutions by OPAP (octylphenyl acid phosphate) and D2EHPA (di-(Z-ethy lhexy1)phosphoric acid) was studied within the context
of stripping with strong HCI such that a saleable waste-fiee iron produa muld be generated
downstream. Operated under ambient extraction and HCI stripping conditions, 0.95 F OPAP
was found to be a highly suitable extractant for the removal of i r o n o kom strong synthetic ZnSO4-&S& soiutions and for the preparation of concentrated iron chioride stnp solutions.
Its major advantages included: very low sulphate co-extraction; reasonable zinc coextraction; very low chloride back-extraction; and suficient iron build-up and acid balance when a 'moderate strength' HCI-FeC12 strip feed (3.38 N HC1-58.5 g/L F e 9 . 7 g/L Fe(m)) was used. Certain advantages were exhibited by 1.25 F D2EHPA over 0.95 F
OPAP. These included a greater relative stability in aqueous streams, slightly better
~ e ~ + / ~selectivity, n'+ and a comparable iron(IIi) loading capacity (-20 g/L) when operated at
50C. However, major drawbacks with D2EHPA were identified which included significant
mlphate co-extraction (approximately twenty times greater than 0.95 F OPAP) and ineffecive stripping and hence p w r iron build-up (-100
fi)with the 'moderate strength'
strip feed.
L'extraction par solvant du
de solutions de procd d'extraction de zinc via
l'utilisation d70PAP et de DZHPA a t tudie dans un environement de recouvrement haute concentration d'acide chlorhydrique, le but tant de gnrer une produit de fer exempt d'impurets et valeur commerciale, plus loin au cours du procd. Dans des conditions ambientes de r-extraction et de recouvrement l'acide chlorhydrique, I'OPAP 0.95 F s'est
avr hautement efficace a I'extrxion de fer@) d'une solution synthktiquz de ZnSOr
H2S04 forte concentration, et la prparation de solutions de r-extraction concentres de
chlorures de fer. Les principaux avantages sont: une trs faible CO-extractionde sulphates; une m-extraction de zinc acceptable; trs peu de r-extraction de chlorures; une accumulation sufisante de fer et une bonne balance d'acide quand une solution modrment forte d'HCLFeCI2 (3.38 N Hel-58.5 g/L F-9.7
g/L F m ) est utilise comme solution
de rextraction (source). Le 1.25 F D2EHPA comporte certains avantages relativement au

0.95 F OPAP, tels qu'une meilleure stabilit dans les dplacements aqueux, une meilleure
slectivit ~ e ~ + / et ~ une n ~capacit + d'absorption de
fera comparable (-20 f i )lorsque

CO-
utilis a 50C. Il existe toutefois des cots ngatifs l'extraction au DZEHPA tels qu'une
extraction importante de sulphates (-20 fois plus qu'avec I'OPAP 0.95 F), et une rextraction inefficace, causant une pitre accumulation de fer (<cl00f i )avec l'utilisation de la solution de rextraction (source) modrernent forte.
My deepest appreciation goes to Professor G.P. Demopoulos for the valuable lessons that 1
learned under his supervision. His passion for learning has been a great inspiration for me. Hopefully, an opportunity will corne in the fture to w o r k together again. The Natural Sciences and Engineering Research Council of Canada is gratefully acknowledge for providing financial support. Special thanks Monique Riendeau for providing invaluable assistance and answers to an endless number of questions conceming analytical methods. Thanks goes to Ed Siliauskas fiom the Department of Chernical Engineering who helped develop su many ICP methods for my work.
1 am very grateful to Trina for providing valuable cornments on the writing of this
manuscript and more. Thanks also to Dimitrios (at McGill and NTC) and former NTC colleagues (Terry Murphy, Serge Monette) who offered helpful encouragement and assistance.
1 feel especially privileged to have been part of such a talented and personable group as that
of the Hydromet Lab. It refleaed the best of what the hydrometallurgical indu-
is and
what it t d y can be. 1 appreciated very much the international flavour that existed in the
group, especially being one of the few Canadians in it! The w a m welcome for my family
during their visit was so much appreciated. 1 am indebted to al1 the gang for many reasons:
Amy, Nielq Stacey, and Dave for the many helpful discussions; Sid for her inspiration and
tremendous energy; Trina, Georgiana and Qiankun (the other 'family-man') for their great professionalism; and Terry for al1 sorts of help that he supplied me.
Thanks also to Cam1 Rousseau, Ray Langlois, and the rest of the staff as well as grads such as James (for the coffee visits) and the undergrads who dl made the university feel not so big. Much thanks to Louis for his Eendly lab visits and for his help with the translations.
TABLE OF CONTENTS
ABSTRACT ............................................................................................. III RSUM ................................................................................................. N ACKNOWLEDGEMENTS ............................................................................ V TABLE OF CONTENTS ............................................................................... W LIST OF FIGURES ..................................................................................... X LIST OF TABLES .................................................................................... X v 1 INTRODUCTION
..................................................................................1
1.1 INDUSTRIAL ZINC PRODUCTION .......................................................... 1
................................................... 1 1.1.2 Present iron rejectionpractices m i p r oblems ......................................... 2 1.2 IRON SOLVENT EXTRACTION ............................................................ 3
1.1.1 Roast-Zeach-electrowinprocess 1.2.2 Conceptual integration N>iothe zinc process jlwsheet ............................... 4 1.3 RESEARCH OBECTIVES ..................................................................... 6 1.3.1 &actants
under shrdy ................................................................... 6
1.3.2 Main objective .............................................................................. 6
2 LITERATURE REViEW AND THEORY
1.3.3 mesis outhe ................................................................................ 6
.....................................................8
2.1 I R O N 0 REMOVAL USmG DZEHPA AND OTHER EXTRACTANTS ............ 8 2.1.1 Cornpmson o f ironflll) l w d n g and stripping characteristics .......................8 2.1.1.1 Extractant solubility and stability ...................................................... 8 2.1.1.2 E x t r a d a n t pH fnctionaliiy ............................................................. -10 2.1.1.3 Extradion kinetics and ~ e ~ ' / ~ n selectivity " ......................................... 12 2.1.1.4 Loading capacities and isotherms ...................................................... 13 2.1.1.5 Iron(m) stripping ......................................................................... 14 2.1.2 Generic d ~ f l a l t i e ......................................................................... s
16
2.1.2.1 S O and ~ Cr carry-over and possible remedial saubbing measures ............. 16 2.1.2.2 hadequate iron(m) build-up and possible supplernentary concentration ........ 21 2.2 DOWNSTREAM iRON OXIDE PRODUCTION .......................................... 24
2.2.2 Fluidid-bed rwrter pyohy&olysis ................................................... 24 2.2.3 Spray roaster pyrohydrolysis ............................................................. 25
3 . EXPEREW3NTAL ................................................................................. 26
...................................................................................... 26 3.2 EXTRACTANT PREPARATION ............................................................ 28 3.2.1 OPAP preparation ......................................................................... 28 3.2.2 D2EHPA andM2EHPA preparation ................................................... 28 3.2.3 Condironing of p r e p e d extractrmtr ................................................... 29 3.3 ANALYTICAL METHODS ................................................................... 29 3.3.1 F r e e a c i d t i t r a t i o m ........................................................................ 29 3.3.1.1 Extractant concentration adjustment of freshly prepared organic solutions ...... 29 3.3.1.2 F m acid determinations in expenmental aqueous sarnples ........................ 30 3.3.2 Totalzron(ll,I . titratim ................................................................ 30 3.3.3 rgunic smnple una&sis .................................................................. 31 3.3.4 Induciveiy coupled plama spectroscopy (ICP) ....................................... 32 3.3.5 Ion chromatography (IC)................................................................ -32 3.4 EXPERIMENTAL PROCEDURES AND SET-UP ........................................ 32 3 .4.1 Extractant solubility m>d stabili~v tests ................................................. 32 3.4.1.1 Extractant conditioning and solubility in pure H2S04and HCI solutions ........ 32 3.4.1.2 Extradant solubility in aqueous feed and strip solutions ........................... 32 3.4.1.3 Long-term degradation tests ............................................................ 33 3 .4.2 Extraction tests .......................................... . . ............................ 34 3.4.2.1 Extraction kinetics tests ................................................................. 34 3 .4.2.2 Extraction isotherms .................................................................... - 3 4 3.4.3 Sbippngtests .............................................................................. 34 3.4.3.1 Stripping kinetics tests .................................................................. 34 3.4.3.2 Stripping isotherms ..................................................................... - 3 5 3.4.4 E x p r i m e n t a l set-ups ..................................................................... 35 3.4.4.1 Long-term degradation tests ............................................................ 35 3 A4.2 Solubility, extraction, and stripping tests ............................................. 36 3.4.4.3 Extractant wnditioning and pre-loading preparations ............................. -37
3.1 REAGENTS
vii
4 0 ICESULTS AND DISCUSSION
o o o o ~ o o a o o o o o o e a o o a o o o o o ~ o o e o a o o o o o ~ o o o o o o o a o o e e o
39
4.1 EXTRACTANT SOLUBILITY AND STABILI'IY
....................................... -39 4.1.1 Fresh extructant conditioningand solubiky .......................................... 40 4.1.1.1 Extractant conditioning and solubility in pure H2S04and HCI solutions ....... 40 4.1.1.2 Extractant solubility in aqueous feed and stnp solutions ........................... 44 4.1.2 Long-lem &gradation reeslts .......................................................... -46 4.1.2.1 Extractant stabilities ...................................................................... 47 4.1.2.2 Effect of temperature on degradation ................................................. 49 4.1.2.3 I r o n o aitaiysis of ester hydrolysis ................................................. -50 4.2 OPAP AND D2EHPA EXTRACTION ......................................................-54 4.2.1 &traction kinetics and eficiency ........................................................54 4.2.1.1 E f f e c t of acid concentration and temperature on o n o extraction eficiency. 55 4.2.1.2 Zinc co-extraction as a fnction of time .............................................. 56 4.2.1.3 Sulphate cwxtradion as a function of tirne ......................................... 57 4.2.2 ~ e ~ + / Z hmrd l + F~~+/so:extraction selecfivity ....................................... 57 4.2.2.1 Effect of acid concentration on ~ e ~ ' / ~ selectivity n~' ...............................58 4.2.2.2 Effect of temperature on ~e~+/zn'* selectivity ....................................... 59
4.2.2.3 Effect of acid concentration and temperature on F ~ ~ + I Sselectivity O ~ ~ - .........-60 4.2.2.4 Electronic and stenc effects conducive to high F ~ ~ + / s selectivity o~" ............ 61
4.2.3 IronflII)Z d n g chmacterislics ......................................................... 63

4.2.3.1 Phase separation characteristics under extraction conditions ...................... 63 4.2.3.2 Maximum workable extractant concentrations ...................................... -64 4.2.3.3 I r o n o extraction isotherms ...........................................................65 4.2.4 ~ + r m d ~ ~ ~ ~ ~ ................................................................. m r b b i n ~ 67 4.3
OPAP AND D21EWPA STRIPPING ........................................................... 70 4.3.1 ShclPping kinetics i d eficiency ......................................................... 71 4.3.1.1 Stripping kinetics ........................................................................ 71 4.3.1.2 m e c t of acid concentration on stripping efficiency ................................. 72 4.3.2 Stripping characteristics ................................................................. 74 4.3.2.1 Phase separation characteristics under stripping conditions ........................ 74 4.3.2.2 I r o n o stripping isotherms ............................................................ 75
viii
.............................................................. 76 4.3.3 EffectufFeCIz onst~pping

4.3.3.1 Ef'ect of FeC12 on stripping kinetics and efficiency ................................ 76 4.3.3-2 Impact of FeClz presence on stripping isothem .................................... 80
4.3.4 @erimental ven$catratron o f material balance findings: 'Moderate strength ' acid stripping .............................................................................. 83
4.3.4.1 Mass balance results ..................................................................... 84 4.3.4.2Experimental results and cornparison with simulation data ........................ 85 4.3.5 ~ n ~ + d ~ ~ ~ ~ ~ - ~ v e r t o s ........................................... t n p s o l u t i ~ ~ t ~ 88 4.3.5 .1 Carry-over using pure HCI solution as strippant ..................................... 89
....................................... 89 4.3.6 Ct carr)cover to orgunic phare ......................................................... 90 4.3.7 Nibic acid stripping ........................................................................ 93
4.3.5.2 Effect of FeC12 on 2n2+and SO? carry-over
5. CONCLUSIONS AND RlECOMMENDATIONS
...........................................
96
5.1 CONCLUSIONS ................................................................................. 96 5.2 RECOMMENDATIONS FOR FUTURE WORK ........................................... 98
APPENDIX A MODIFIED FREE ACID TITRATION METHODOLOGY
...........105
113
113
A 1 Free acid determination in strong H2SOcF~(SO4h-ZnSOqa ........................ 105

A2 Free acid determination in strong HCI-FeC13(-FeC12)w ................................ 110
APPENDIX B IRON(III) COORDINATION WITH S O ~ ;PO^^, AND RzPOli* B .1 Stability constant data ........................................................................ B.2 Selection and treatment of thermodynamic data .......................................... B.3 Generated stability constant findings ...................................................... B.4 Ligand substitution kinetics .................................................................
APPENDIX C CONCEPTUAL INTEGRATED IRON SX-ZINC PROCESS
114 116 119
FLOWSHEET .................................................................................121
C.1 Material balances ............................................................................. 121
C.2 Concephial electro-assistecl stripping electrochemical data ............................. 129
C.3 Preliminary operating cost analysis ......................................................... 130
LIST OF FIGURES
Figure 1.1: Conventional zinc roast-leach-electrowin process flowsheet........................ 2 Figure 1.2. Conceptual integrated FeSX-zinc roast-leach-electrowin process flowsheet...... 4 Figure 1.3 : Iron solvent extraction stages in the conceptual fiowsheet........................... 5 Figure 2.1 : Extraction of iron(m) fiom H2S04solutions with organophosphonis extractants (data fiorn Dernopoulos et al. 1993)........................................ 11 Figure 2.2: Extraction of iron(III) fkom H2S04solutions with 10% v/o D2EHPA and 20% d o M2EHPA; A/O=l. 50C. AF = 25 g/L ~ e ~data + ; fiom Delmas et al. 1996. Demopoulos et a L 1989.1996 .............................................. 12 Figure 2.3 : Extraction of iron(IiX) fiom aqueous solutions containing sulphuric acid 'O'. hydrochlonc acid 'A'. and nivic Acid 'O' with 0.05MDZEHPA in kerosene at 20C (reproduced from Sato et a L 1985)................................ 14 Figure 2.4: Imn(m)-sulphate speciation diagram at 50C (0.5 M ~ e ~ 3 (constructeci with algorithm developed by Filippou et aL 1993) ................... 17 Figure 2.5: I r o n o chioride speciation diagram at 20C ( l u 3M ~ e ~ 3 (reproduced fkorn Aprahamian and Dernopoulos 1995).............................20 Figure 2.6: I r o n o electro-reduction step interposed between solvent extraction stripping and pyrohydrolysis............................................................ 23 Figure 3.1 : Structural formulae of D2EHPA (Rl=R2=R3).M2EHPA (Ri=&; RFH). and OPAP (50% Rl=R2=& and 50% Ri=% R2=w molar basis)................. 28
Figure 32:Schematic of experimental apparatus for solubility. extraction, and

stripping tests..............................................................................36
Figure 3.3. Schematic of pump-mix designtype impeller........................................ 3 7
Figure 3.4. SX mixer apparatus...................................................................... 38 Figure 4.1 : Conditioning of fiesh extractants (0.95 F; N e 1 .0. 10 minutes/contact): (a) 50 g/L H2S04 at 50C; (b) 6 N HCl at 20C...................................... 41 Figure 4.2: Conditioning of fiesh extractants (0.95 F;A/O=1 .0. 10 minutdeontact): (a) OPAP;(b) D2EHPA ................................................................. 41 Figure 4.3 :Extractant sdubility kinetics of OPAP and D2EHPA (0.95 F) under loading and stripping Conditions...................................................... 45
Figure 4.4: mect of metal-salts on aqueous solubility of fresh extractants (0.95 F): (a) OPAP; (b) D2EHPA ............................................................... 46
Figure 4.5: Long-term degradation of OPAP and D2EHPA (0.95 F) in aqueous feed ' , g/L, 2n2+,50 g/L H2S04): Solution (A/=1.0; AF= 25 g/L ~ e ~ 90 (a) 20C; (b) 50C. ........................................................................ 48
Figure 4.6: Long-tem degradation of OPAP and D 2 m A (0.95 F) in stnp feed solution (O/A=1.0; SF=40 g/L F$+, 6 N HCI): (a) 20C; (b) 50C. ...............48 Figure 4.7: Postulateci mechanism for i r o n o catalyzed hydroly sis of organophosphoric acids (based on Henderson 1993). ................................ 51 Figure 4.8: Stabilizing inductive effect on extractant molecule by loaded ironw). ..........52 Figure 4.9: Iron@I) extraction kinetics for: (a) 0.95 F OPAP; @) 1.25 F D2EHPA, (A/O=2.0; no acid control). .............................................................. 56 ~ n ~ + as a fundion of initial acidity Figure 4.10: OPAP (0.95 F) ~ e ~ + /selectivity (A/0=2.O). ............................................................................... 58 Figure 4.1 1: 0PAP(0.95 F)-D2EHPA(1.25 F) cumparison of ~ e ~ ' / ~selectivity n~' as a function of initial acidity (A/O=2.0): (a) 20C; (b) 50C. ....................59 Figure 4.12: OPAP (0.95 F) F~~'/so? selectivity as a function of initial acidity ( A f M . 0 ) ............................................................................... . 60 ~~Figure 4.13: 0PAP(0.95 F)-D2EHPA(1.25 F) cornparison of F ~ ~ ' / s oselectivity as a function of initial acidity (A/=2.O): (a) 20C; @) 50C. .................... 6 1 Figure 4.14: Conceptual i r o n o oaahedron in a non-equilibrium loaded organic phase containing di-al ky1organophosphoric acid extractant. .................... .62 Figure 4.15: I r o n o extraction isothenns for OPAP and D2EHPA (no acid control). ..... .66
Figure 4.16: I r o n o extraction isothems for 0.95 F OPAP: (a) 20C; (b) 50C; (LO = loaded organic; AF = aqueous feed; SO = stnpped organic; no acid control). ......................................................................... 67
Figure 4.17: Iron(m) stripping kinetics for: (a) 0.95 F OPAP; @) 0.95 F D2EHPA, (20C, O/A=.50; ~e~+I-~=18.3 g/L (OPAP) and 13.8 g/L (DZEHPA); no acid mntrol). ........................................................................ .7 1
e c t of hydrochlonc acid concentration on iron(m) stripping; Figure 4.18: m (2SC; O/A=1.O; 1.9 F ( 6 % d o ) D2EHPA; @?e3fl,=28.0 @L; no acid wntrol) (data taken f?om Sahu and Das 1997). .............................. .73
Figure 4.19: I r o n o distribution in OPAP or D2EHPA and hydrochloric acid at 20C: O/A=.SO; [~e~T,=l8.3 g/L (0.95 F OPAP) and 13.8 gR.(0.95 F D2EHPA); 5 minutes contact time; no acid control; (0.05 F DZEHPA data taken fiom Sato et aL 1985). ...................................................... 74 Figure 4.20: Stripping isotherms using 6 N HCI (initial acid) at 20C for: (a) 0.95 F OPAP; @) 1.25 F D2EHPq (no acid control); (LO = loaded organic; SF = strip feed; SL=strip solution; SO = mipped organic). ....................... 75 Figure 4.21: Effect of FeC12 on i r o n o stripping kinetics for: (a) 0.95 F OPAP; @) 0.95 F D2EHPA; no acid control; (20C, O/A=.50; peTaeo= 18.3 glL and 13.8 g/L for OPAP and D2EHP4 respectively). .................. 77 Figure 4.22: Iron@,IIl) solubility data at 20C: (a) FeCb-HCI-H20 and FeCh-HCl-H20; (b) FeC13-FeC12-H20;(Silcock 1979). .......................... . 7 8 Figure 4.23: Effect of aqueous chioride concentration on 0.95 F OPAP and 0.95 F D2EHPA stripping distribution coefficients at 20C; (O/A=0.50; [~d7,~=18.3 g/L (OPAP) and 13.8 g/L (D2EHPA); 5 minutes contact time; no acid control). ................................................................. -79 Figure 4.24: Enect of iron(I1) on stripping isotherms using 6 N H C I at 20C for: (a) 0.95 F OPAP; @) 1.25 F D2EHPA, (no acid control); ~e'7,.= 21.6 glL, 21.3 g/L (OPAP) and 19.5 g/L, 20.1 g L (DZEHPA). .................. 81 Figure 4.25: Stripping isotherms using 6 N HCl-70 g/L F e @ ) at 20C for: (a) 0.95 F OPAP;@) 1.Z F D2EHPq [R3Tqo=2 1.6 g/L (OPAP)and 19.5 glL @2EHPA); no acid control; (LO = loaded organic; SF = strip feed; SL=strip solution; SO = stripped organic). ......................................... .82 Figure 4.26: HCI and total iron(I1,m) concentrations associated with a closed acid loop (refer to Appendix C mass balance conditions and assumptions). ......... 84 Figure 4.27: M a s balance flowsheet involving a closed acid loop iron SX integrated 200,000 tpy capacity zinc plant; (refer to Appendix C m a s balance conditions and assumptions); (HALO/F=hot acid leach overflow; LO = loaded organic; Rec.Org=recycled organic; SF = strip feed; SL=strip solutioq redSl=reduced strip solution; SO = stripped organic). ................. 85 Figure 4.28: Total i r o n o stripping isothems using 'moderate strength' strip feed at 20C for: (a) 0.95 F OPAP;@) 1.25 F D2EHPA; SF=3.38 N HCI, 58.5 glL F e @ ) , 9.7 g/L F e o ; [~df1,,=20.9 g/L (OPAP) and 19.7 g/L,(DZEHPA); no acid control; &O = loaded organic; SF = strip feed; SL=stnp solution; SO = siripped organic). ................................................................ 87
Figure 4.29: I r o n o stripping isothems using 'moderate strength' strip feed at 20C for: (a) 0.95 F OPAP; @) 1.25 F D2EKPA; SF=3 -38 N HCI, 58.5 g/L FeO, 9.7 g/L F e o ; pe3+Jars,=20.9 g/L(OPAP) and 19.7 g/L @2-A); no acid control; (LO = loaded organic; SF = strip f d ; SL=strip solution; SO = stripped organic). .......................................... 88 Figure 4.30: Zinc and sulphate carry-over to the strip solution Eom unscrubbed loaded organic at 20C: (a) zinc; (b) sulphate; O/A=.SO; [~d+],~= 18.3 g/L (0.95 F OPAP) and 13.8 g/L (0.95 F DZEHPA); no acid control. .....90 Figure 4.3 1: Chloride back-extraction during stripping: a) phase ratio eEect (20C; 6 N HCl equilibrium acidity); b) strip feed eEea (20C; O/A=1.0; no acid control)............................................................................. - 9 2 Figure 4.32: Sripping isothems using 4 N HN03 at 50C: pe37,.=l 1.3 g,A,(0.53 F OPAP) and 11.5 g/L(0.62 F D2EHPA); no acid control; (D2EHPA data taken from Van Weert et al. 1998). ................................................... 94 Figure B. 1: Stability constants as a fundon of molar ionic strength. ........................ .117 Figure B.2: Estimation of the stability constant for Feo-D2EHPA at infinite dilution (data taken nom Guseva et al. 1972). .................................... ,118 Figure C. 1: Mass-balance conditions giving closed acid loop with 3.88 N HCI strip feed. ............................................................................... L23 Figure C.2. Mass-balance conditions giving closed acid loop with 4.38 N HCI strip feed. ............................................................................... 124 Figure C . 3: Mass-balance conditions giving closed acid loop with 4.88 N HCI strip feed. ............................................................................... 125 Figure CA: Mass-balance conditions giving closed acid loop with 5.38 N HCI strip feed. ............................................................................... 126 Figure C.5: Mass-balance conditions giving closed acid loop with 5.88 N HCl strip feed. ............................................................................... 127 Figure C.6: Mass-balance conditions giving closed acid loop with 5.93 N HCI strip feed. ............................................................................... 128
LIST OF TABLES
Table 2 . 1: E x t r a c t a n t solubilitydegradation (Dernopoulos et al. 1996. Ritcey et al. 1975. Lakshmanan et al. 1996)............................................ 9
Table 2.2: E x t r a c t a n t cornparison of i r o n o loading characteristics 2. 1996. Lakshmanan et al. 1996)...........12 @emopoulos et uL 1996. Delmas et a Table 2.3: Exractant cornparison of iron@I) stripping characteristics @emopodos et a 1.1996. Delmas et UL 1996. Lakshmanan et al. 1996)........... 15 Table 2.4: Evidence of sulphate and chloride catry-over (Dernopoulos et al. 1996. Van Weert et 4L 1998. Lakshmanan et al. 1996)...................................... 18 Table 3.1. Inorganic reagents used in experimental work ....................................... 26
Table 3.2. Organic reagents used in experimental work ..........................................27
Table 3.3. Impurities present in received extractants as declared by suppliers................ 29 Table 3.4: Major equipment used in extractant solubility. loading, and stripping tests......................................................................... 37 Table 4.1 : Cumulative losses after 7 contacts with fiesh 50 g/L H2S04 .0. 10 minutes/contact)................................................... 42 (50C; Table 4.2. Sulphuric acid conditioning of Albright & Wilson M2EHPA (0.95 F) batch..... 42 Table 4.3. Extractant baseline ofaqueous solubilities during acid washing.................... 44 Table 4.4. Extractant solubility in finate
and strip solutions (A/=l.O). ................... 45
1.O). ......... 49
Table 4.5. Extractant solubility-degradationin aqueous and strip feeds (A/*
Table 4.6. Zinc loading ( A / M . O . pIS04]o= 50 g/L)............................................57

Table 4.7. Sulphate loading (A/O=2.0. [H2S04],= 50 &) ...................................... 57 Table 4.8. Evaluation of zinc-loaded OPAP sarnple scrubbing (20C; O/A= .50)............ 68 Table 4.9. Evaluation of sulphate-loaded OPAP sarnple scrubbing (20C; O/A= .50).......69
Table 4.10: Equilibnum stripping performances of OPAP and D2EHPA at O/A*.O; (0.95 F OPAP: 20C. SOC; 21.6 g L ;20 minutes contact t i m e ; no acid control); (0.95 F D2EHPA: 20C; pe3C],, = 13.8 g/L; 30 minutes contact t i m e ;no acid control).......................................................... -79
ma,,=
xiv
Table 4.11: Ef5ect of i r o n o on V o n o build-up in the strip solution at O/A=10; (20C; ~d+l,~=21.6 g/L, 2 1.3 glL (OPAP) and 19.5 20.1 giL (DZEHPA); no acid control). ........................................................... 8 1
a,
Table 4.12: Effect of bon@) on total iron(II,m) build-up in the strip solution at O/A=10; (20C; [~df1,=2 1.6 gR,2 1.3 g/L (OPAP)and 19.5 g/L, 20.1 gR.@2EHPA); no acid control). ............................................... .82
Table 4.13 : M a s balance simulation-OPAP experimental results cornparison of strip solution compositions in 'moderate strength' acid stripping (20C). ............. 86
Table 4.14: Molar ratio of loaded Cr and ~ e ) ' in stripped OPAP and D2EHPA at 20C....................................................................................... -92 Table 4.1 5: Zinc and sulphat e carry-over to strip solutions at 50C (O/A=.50). ............ .95 standards 0 Table A 1: Preparation of 250 mL H 2 S O ~ - F ~ ( S O & - Z n S ('A7=acid only; 'AFZ7=acid+ i r o n o and zinc sulphates). ................... 106 Table A2: Titration analysis of H 2 S - F ( S O 4 n S 0standards ('AY=acidonly; 'AFZ'=acid + iron(m) and zinc sulphates). ..................... 107
........................... 1 13 Table B. 1: Equilibria in the aqueous system F~~'-OH.-SO~--PO~*.

Table B.2:Selected thermodynamic data for the aqueous system F~'-OK-SO~~-PO?-; data taken fiom Smith and Martell (1976-7), Sillen and Martell (1964, 197l), Hogfeldt (1982), Kotrly and Sucha (1 985), Bamer and Scheuerman (1987), Naumov et al. (1 974), Robins et al. (199 1), Robins (1990), Khoe and Robins (1988), and Filippou et al (1995). ...................... 115 Table B.3 : Calculation of equilibrium thermodynamic data. .................................... 116
Table B.4:Calculated stability constants. ......................................................... 117

Table C. 1: Estimation of electrode operating potentials (data fiom Liao 1997). ........... 130 Table C.2: Preliminary operating balance sheet @rice estimates from Bialko 1998, Houlachi 1998, Pape 1998, Poy 1998). ............................................... 131
1. Introduction
1 . INTRODUCTION 1.1 INDUSTRIAL WNC PRODUCTION
1.1.1 Rout-leach-electrowin process (RLE)
The roast-leach-electrowin (RIE) process is responsible for approximately 85% of the world's prKnary zinc production (Kajiwara et al. 1995). The RLE feed, a zinc sulphide concentrate (52% Zn, 7% Fe) is first roasted to drive off sulfbr, producing a readily
h e conventionai RLE flowsheet is given in Figure 1.1. The solubilized Z n 0 calcine. T

calcine (60% Zn, 10% Fe) is then subjected to a weak acid 'neutral leach' (NL) which solubilizes the oxide component of the calcine (Equation 1.1). The neutral leach pH is raised
in a stepwise manner so tha iron hydrolysis occurs. This precipitates iron as an morphous
hydroxide, which dong with the insoluble zinc femte reports as a residue feed to the high acid leach (HAL). In order to optimize zinc recovery, the HAL unlocks the remaining unleached zinc by forcing dissolution of this zinc ferrite-containing residue under high
h i s consequently dissolves dl the temperature and strong acid conditions (Equation 1.2). T
iron present in the residue. This uon must be rejected prior t~ recycling the rwvered zinc as
zinc sulphate solution to the leach. Inis is done via hydrolytic precipitation (e.g. jarosite,
JAR) which generates leach acid (Equation 1.3). The generated iron waste residue is then
stockpiled.
The neutral leach supernatant zinc sulphate solution contains metals other than zinc which
were additionally solubilized (including Cu, Cd, and Co). This impure solution undergoes purification (Equation 1.4) prior to electrowinning (Equation 1.9, ultimately yielding the
final zinc product
1. Introduction
Zn Calcine (60% Zn, 10% Fe)
I 1 1
i NL: neutral leach

I I
I
I
1 I
j PUR: purification 1 [ EW: electrowinning i :HAL: hot acidleach i

I
Figure 1.1: Conventional zinc roast-leach-electrowin process flowsheet.

1.1.2 Preseat Von rejection pirctices and problems
Hydrotytic precipitation of iron as a means of iron rejection is presently being employed in

25 zinc plants worldwide. Jarosite is the most cornmon uon waste residue, being produced
by 18 plants while goethitelparagoethite and hematite are produced at 6 and 1 plant(s),

respectively (Ashman, 1996). Iron rejection is a major problem in the zinc industry. With the exception of hematite, iron waste residues are notably voluminous, comprised only of 2 5 4 % iron, as well as being produced in very large quantities, e.g. 4 . 5 ton jarosite produced per ton Zn metal. These residues have an inherent toxicity due to the entrainment of toxic metal irnpurities which occurs during precipitation, and results in the residues being classified as 'hazardous industriai waste'. Consequently, jarosite and goethite are presently stockpiled in expensive groundwater secure tailings ponds. serious doubt. However, environmental regulations are becoming increasingly more stringent, placing the future issuing of permits for new tailings ponds in
1. Introduction
Various efforts such as 'jarofix' (Rosato and Agnew 1996) to improve or modifi the
performance of present iron precipitation-disposal technologies have reduced the adverse effects on the environment. However, al1 these approaches at best tend to be short or medium-tem solutions. A longer terni solution is needed which involves a quantum leap in extraction technology that would lead to the iron waste-fiee production of zinc. This implies that an iron by-product would have to be obtained fiom zinc sulphate process solutions that is
of acceptable saleable quality for downstream use in other industrial sectors. The value
obtained for the iron oxide would be vital as the anticipated increase in production costs would have to be counterbalanced. To obtain such an 'advanced' produd &om such an ultra-concentnited wmplex industrial solution, a powedl separation process is needed that can cleanly remove and concentrate iron out of the zinc process solution. Solvent extraction (SX) is the only separationconcentration method that can handle such large volumes of concentrated solutions, and hence the interest in the development of an iron solvent extraction process.
1.2 IRON SOLVENT EXTRACTION
Rosato and Agnew (1996) surveyed a total of 25 options for potential long-term iron removal technologies as alternatives to present iron precipitation-disposal practices in the zinc industry. Among them, solvent extraction is one option under consideration as a possible route. To date, no extractant has been found or adequately developed which meets al1 the essential criteria, which are given below.
1.2.1 Cntena for estractant selection
For an iron solvent extraction process to be integrated into an RLE process, the following technical requirements for the extractant will have to be met:
1 .
High iron loading capacity directly fiom the acidic zinc feed without pH control. High total iron build-up in strip liquor (X g L ) for the technical and mnornic
viability of downstream iron by-product processing. Minimal C l - cany-over and solvent loss to raffinate in order to avoid the
2.
3.
catastrophic effcts to downstream electfowinning, i.e. loss of m e n t efnciency.
1. Introduction
4. 5.
Minimal S camy-over to the strip liquor to ensure uon by-product purity.
Minimal organic losses to aqueous streams to controi solvent costs.
The anticipated iron by-product can be a femc oxide of acceptable physico-chernical quaiity. T h i s implies that there must be low contamination of S, 2 n 2 ' , and other impurities in the
solution feed to the iron oxide producing process.
1.2.2 Conceptuai integration into zinc process flowsheet
The possibility of integrating solvent extraction into an existing zinc process flowsheet for the purpose of producing a marketable iron by-product was discussed by Piret and Melin (1993). Figure 1.2 is a simple flowsheet depicting the conceptual introduction of iron solvent extraction into a zinc RLE circuit. Solvent extraction coupled with pyrohydrolysis, an iron
oxide producing process, replaces the jarosite precipitation-disposal pairing in the conventional flowsheet (Figure 1.1). A saleable iron oxide is produced while the stnppant acid, H C , is regenerated and recycleci.
Z n Calcine (60% Zn,10% Fe)
,*"'-""--"----""'--------'--**-*----*--.*----
* i NL: neutral leach PUR:purification . 1 EW: electrowinning 1 i. HAL: high acid leach / j PH: pyrohydrolysis f
8
t
r I
Saleable Fe203
Figure 1.2: Conceptual integrated FeSX-zinc roast-leach-electrowin process flowsheet.
1. Introduction
More specifically, as shown in Figure 1.3, the hot-acid leach solution (HAL), composed approximately of 25 g/L ~ e ~ '90 , g/L 2n2+,and 50 g/L H2SO4 (-250 g/L SOC in total),
becornes the feed to the loading stage of solvent extraction. The generated raffinate is
envisioned to contain approximately 5 g/L ~ e and ~ 75-100 + g/L H2SO4 assuming there is no neutralization during solvent exraction. The residual iron content is desired in this recycle strearn as iron acts as a vitai impurity scavenger while it hydrolyzes in the neutral leach. T h i s lightens the burden upon purification, the quality of which downstream electrolysis depends. Acidification of the raffinate, as a result of the cation exchange reaction (Equation 1.6), takes place upon uon extraction where the bars denote the organic phase.
HAL O F
4AQUEOUS FEED PHASE
iLeach i
Figure 1.3: Iron solvent extraction stages in the concephial flowsheet.
T h i s generates more acid than jarosite precipitation (Equation 1.3). Consequently, direct
recycling of the rafnnate to the neutrai leach, as is done in conventional zinc leaching circuits
that reject iron as jarosite, carmot be done. Therefore, it would be necessary to partially
neutralize the rattinate fiaction that is recycled to the leach to pH -1.5 with lime or
1. Introduction
limestone, as is done in the Hernatite Process operateci by Akita Zinc Company (Onozaki et al., 1986). A sulphate bled would be necessary? as given in Equation 1.7, because it is not inherent in the process in contrast to the jarosite process.
Upon stripping of the loaded organic phase with strong HCi, a concentrated iron chlorideHCl stnp solution of sufficient tenor (NO0 g/LFe) and purity is the targeted feed to a fluidued bed (Peek et d 1996, Poy 1996) or spray roaster (Kamer 1986) pyrohydrolyser. Here the solution is converteci to clean and HCI, the latter being recycled to make-up
the strip solution in the stripping stage of solvent extraciion (Figure 1.3).
1.3.1 Extractants under study
The extractants, octylphenyl acid phosphate (OPAP) and di-(2-ethylhexyl)phosphoric acid

(D2EHPA), which are both memben of the organophosphoxus extradant family, were studied. OPAP is a cornrnercially available extractant which was previously investigated as a candidate for gallium extraction from acidic solutions (Mihaylov and Distin, 1995). It has yet to be investigated for i r o n o removal. The commercial availability and acceptance of
D2EHPA in present practice makes this extractant a useful reference against which to
evaluate OPAP. As well, due t o the absence of data relevant to this specific application, it remains an unconfirmed candidate which w a r r a n t s investigation.
13-2 Main objective
a
To test and assess the technically viability of candidates OPAP and D2EHPA in terms of solubility-degradation, extraction, stripping, and selectivity characteristics within the
context of an integrated FeSX-Zn RLE flowsheet.

1.3-3 Thesis outiine
a
Chapter 2 critically reviews previous research pdomed on iron solvent extraction fiom
zinc process solutions fkom the perspective of using strong HCl as the stripping agent.
1. Introduction
Chapter 3 describes the experimentai setups and procedures used to achieve the objective
described.
Chapter 4 reports and discusses the results obtained. Chapter 5 gives conclusions and suggestions for future work
2. Literature Review and Theory

2. LITERATURE REVIEW AND THEORY 2.1 I R O N 0 REMOVA. USING D2EHPA AND OTHER EXTRACTANTS
A number of extractants have been proposed for the extraction of iron from zinc process
solutions (Riveros et al. 1998, Flett and Monhemius 1996, Ritcey 1986) arnong which are the commercial cationic
exttactants: Versatic acid
(Collier et
al.
1986); d i ( 2 -
ethylhexy1)phosphoric acid (D2EHPA) (Van Weert et d 1998, Delmas et al. 1996); monol . 1989, 1996); n-ethyl-decano(2ethylhexyl)phosphoric acid (MZEHPA) (Dernopoulos et a
hydroxamic acid (NED) (Lakshmanan et al. 1996); and an aminomethylene-phosphonic acid
(EU2) @elmas et al. 1996). Versatic acid will not be discussed since it cannot be directly
applied to strong acid solutions, and hence necessitates undesably radical changes to the
RLE process leach stages. NED and EU2, which are novel extractants developed specifically
for this application, are the key contemporary candidates against which MEHPA and
octylphenyl acid phosphate (OPAP) should be evaiuated. The emphasis of work at McGill University with organophosphorus acids has recently shifled fiom M2EHPA studies, dating back 10 years @emopoulos et aL 1989, 1996), to present
D2EHPA and OPAP investigations. Although no longer considered as a candidate for this
application, M2EHPA at the least provides a good basis for performance cornparisons with
D2EHPA and OPAF!
Despite the large body of literature available on DZEHPA, there is a
surprising absence of relevant work using strong HCI as the stripping agent. Studies are also
w m t e d for OPAP, as currently nothing has been published with respect to i r o n o extraction. Apart &om OPAP extraction of gallium (Mihaylov and Distin 1995, Judd and Harbuck 1990), only indium and y t t r i u m studies have been conducted (Kikuchi and
Kamagarni 1988, Green and Harbuck 1995).

2.1.1 Cornparison of iron@I) loading and stripping characteristics
2. t1.1 E x f r m w solubi@and stability
The extent of solvent loss resulting fiom extractant soiubility or degradation is an important
issue in the selection of the best extractant. In addition to the cost involved with extractant
loss, there is zero tolerance for organic transfer to zinc tankhouses. For compatison

purposes, it is mentioned that organic levels in copper solvent extraction raf5nates are on the
order of 20-50 ppm. I n the uranium industry, this might go up to 200 ppm (Solvent Extraaion Workshop 1997). The corresponding tolerance levels in the zinc industry are expected to be much lower. Because of this intolerance, any solubilized or entrained organic will have to be recovered
fiom the raffinate phase. Simple clay treatment as practiced in copper solvent extraction
(Solvent Extraction Workshop 1997) is not considered adequate in this context. Instead, other more costly technologies like activated carbon filtration or the use of steam (50-SOC) and air as practiced in uranium solvent extraction (Key Lake) might have to be considered (Solvent Extraction Workshop 1997).
In pilot work, M2EHPA was found to exhibit high organic losses @pm extractant) in both
aqueous streams, as shown in Table 2.1 (Dernopoulos et a L 1996).
DWIPA losses are
relatively limited at 30 ppm in a somewhat comparable, but dilute non zinc-containing sulphuric acid medium (Ritcey et al. 1975). To explain this difference, relative to DEHPA,
M2EHPA has a lower molecular weight (210.2 versus 322.4) due to having one less
hydrocarbon substituent group, which translates into lower relative molecular hydrophobicity, and hence a higher expected solubility in aqueous solutions. In addition,
M2EHPA appears to be especially susceptible to degradation (Molnar et al. 1989). The

likely degradation mechanism for organophosphorus extractants in acid solutions is ester hydrolysis with the degradation products being ortho-phosphoric acid and alcuhols (Solvent
Extraction Workshop 1997, Cupertino et al. 1994).

Table 2.1: Extractant solubility-degradation (Demopoulos et 'a 1996, Ritcey et al. 1975, Lakshmanan et d 1996).
M2EHPA solubility-degradation is much higher in strong HCI strip solutions as opposed to

&SU4-based raflinates (by a factor of 6). The high solubility of M2EHPA in aqueous
streams (raninate or chloride strip) makes it unsuitable for application in this context.
Hence, the search for members within the organophosphorus extractant family other than
M2EHPA should target candidates exhibiting significantly lower solubility and degradation
behaviour. No data on solubility-degradation of D2EKPA in strong HCl solutions has been

reported.
NED appears to be comparable to D2EHPA (41 ppm in 20% wlw Na2SOd). but other data
raises doubt conceming extractant stability. Long-term degradation as 10% cumulative extractant loss from 10% v/o NED in 20% H2SO4-20%W O 4 strip feed afler 32 days continuous contact at 22OC was reported (Lakshmanan et al. 1996). No pertinent information
s available. regarding EU2 i

Having the largest alkoxy group among the three organophosphonc acid extractants, OPAP
will clearly be less soluble than M2EHPA because of the associated hydrophobicity as discussed above. However, overall OPAP solubility relative to D2EHPA cannot be postulated since the fonner consists of a 1:l molar mixture of mono- and di-elkyl OPAP
21.1.2 EwtractantpHfunctionality
In terms of extraction performance, arnong the organophosphorus extractant fami1y, the

organophosphoric acids such as M2EHPA and DZEHPA are preferred for this application since aqueous feed pre-neutralization is avoided. These members are strongly acidic
extractants. Strong acidity means that the extractant readily dissociates enabling high
loading according to Equation 2.1 even in the presence of high aqueous acidity which is required, Le. good pH fiinctionality.
As alkoxy @ O ) groups replace a l h l (R-) groups in organophosphorus extractants, electronwithdrawing character replaces electron-releasing character (Weininger and Stermitz 1984).
As electron-withdrawing c h c t e r inmeases, the better dispersed, and therefore more
stabilized the negative charge of the dissociateci base becomes. A more stable base anion
means enhanced acid dissociation, Le. stronger acidity. Extraction power therefore follows
the order below which favours phosphoric acid groups:
RsOOH < (R0)RPOOH < (RO)J?OOH < (ROXH0)POOH
phosphinic
phosphonic
phosphonc
Figure 2.1 shows experimental extraction data following this trend. nie phosphonic and
phosphoric acids, PC-88A and D2EHP4 respectively, have their order reversed, which is likely due to experimental error. Cyanex 272 is an example of a phosphinic acid extractant.
Figure 2.1 :Extraaion of iron(m) fiom H2S04solutions with organophosphorus extractants (data fiom Dernopoulos et al. 1993).
M2EHPA is more acidic than D2EHPA and hence operates in a wider and higher acid
concentration range. Iron(III) extraction data as a funaion of HzS04 concentration with

D2EHPA and M2EHPA have been plotted in Figure 2.2 showing this.
Following the above reasoning, a larger alkoxy group than that of D2EHPA should give dialkyl OPAP g r e a t e r expected acid strength and functionality than the former. In addition,
OPAP electron-withdrawing character is M e r enhanced by the presence of the phenyl group which itself is electron-deficient due its unsaturated character.
2. Literature Review and Theorv
6 10% vlo 2EWA
i 20% vlo WEWA
Figure 2.2: Extraction of uon(m) from H2S04solutions with 10% v/o DZEHPA and 20% v/o M2EHPA; A/O=1.O, 50C, AF = 25 g L~ d + data ; from Delmas et al. 1996, Dernopoulos et al. 1989,1996.
2.1.1.3 IWtaction kinetics und ~ d + n n ' +seleciivQ
Extraction kinetics of iron(III) are faster with M2EHPA than with MEHPA, as 5-10 minutes
and 15-30 minutes contact times are required respectively for equilibnum to be attained.
NED is comparable at 10 minutes while EU2 is the fastest requiring only I minute contact
time (Table 2.2).
Table 2.2:Extractant cornparison of i r o n o loading characteristics @emopouIos et al. 1996, Delmas et aL 1996,Lakshrnanan et al. 1996).
(% d o ) 40% M2EHPA 30% D2EHPA 50 50 >lsL 5-10 1 3 4 0 ' 24500 Fe3'/zd' 8-15' 140 ~ ~ n ' @pm) f ] ~ 14 45 Loading capacity (g/L) 3 4 No.stages <os <5 ~ e ~(du + l ~
[Extnictant]-cw Temperatun CC) Contact tirne (min)
40% NED 40 10
15% EU2
50
1'
17.3~ 2'
0.08'
4000-5000 8-15' 15
2
4
'- data for 20.4% vlo NED
- data for 1 M v/o extractant
2. Literature Review and Theoq
~ e ~ + l ~selectivity n'+ follows the order: M2EHi?A > EU2 > DEHPA. Although M2EHPA
hae separation factor well above that of the others, D2EHPA and EU2 load less zinc ont0
the organic phase (8-15 ppm versus 140 ppm zinc in M 2 m A ) . The extraordinary i r o n o
extraction power of MZEHPA should be considered when comparing these selectivities. No
direct ~ e ~ ' / ~ nselectivity '+ evaluation was conducted for NED. However, on the order of 40
pprn zinc CO-extraction can be back-calculateci Eom the residual zinc concentration result of
270 ppm that was reported in a strip solution following one contact with fieshly loaded 40%
VIO NED at O/A=7.0 (Lakshmanan et a L 1996). Aithough zinc extraction occun very quickly, ~ e ~ ' / ~selectivity n~' has been found to be a function of contact time andfor i r o n O loading, reaching optimal selectivity at equilibrium.
As i r o n o loading and solution acidity increase with time, loaded zinc is displaced
preferentially by unioaded ironw).
This behaviour was found with both M2EHPA
(Demopoulos et al. 1989, 1996) and D2EHPA @elmas et al. 1996) which suggests this as a characteristic of organophosphoric acid extractants.
The marked difference in the extraction rates of ~ e ) ' and 2n2' with organophosphonc
extractants is a reflection of the signifiant difference between these two cations in terms of water exchange rates. The water exchange rate for 2nZ' is about five orders of magnitude faster than that of ~ e (Cotton ~ ' and Wilkinson 1988). This inherent slow ligand exchange kinetics for ~ e i ' s~believed to be at least in part responsible for the co-extraction of sulphate
as part of the F $ '
coordination sphere. That is, incomplete exchange of extractant with al1
the alphate ligands in an aqueous iron(m) mlphate octahedron generates iron(m)sulphatoorganic complexes in the organic phase, and hence, CO-extractedsulphate (refer to Appendix
BI2-. 1.4 Luaciing copacities and isothmns
All extraction work ated operates at eithei 40C or 50C with the knowledge that typical
AAL overflow streams cool only to about 40C at the point of subsequent treatment. This
coincides well w i t h M2EHPA extraction performance which necessitates operation at 50C to obtain optimum loading and phase separation results (Dernopoulos et aL 1996).
2. Literature Review and nieory
Due to the high iron content of zinc process solutions, in order to achieve optimal results it is
necessary to use extractants at their highest possible concentrations, as permitted by viscosity
and phase separation limitations. The extractant concentrations cited from the literature
(Demopoulos et al. 1989, 1996; Delmas et al. 1996; Lakshmanan et al. 1996) are 40% v/o
(1.9 F) M2EHPq 30% v/o (0.95 F) DWIPA, 40% vlo NED, and 15% v/o EU2.
Conceming loading capacity, 40% v/o M2EHPA ~nsistently attains 45 g/L i r o n o while
al1 others and predictably OPAP, are at or below 20 g/L (Table 2.2). An exception may very well be 40% v/o NED. However, the pertinent loading capacity data was not clearly indicated by Lakshrnanan et al. (1996). The use of the higher molecular weight extractants
DLEHPA and OPAP as alternatives to M2EHPA therefore involves a notable sacrifice in

loading capacity in favour of lower expected aqueous solubility.
2. tl.5 I m n o stripping
The distribution of i r o n o between DZEHPA and various mineral acid solutions (H2S04,
HCl, and HN03) is shown in Figure 2.3. According to this data, H2S04 and HCl at an acid
strength of at least 3 M, or preferably close to 5 M, would be appropriate for iron stripping.
Figure 2.3 : Extraction of i r o n o from aqueous solutions containing sulphunc acid '0 ', hydrochioric acid 'A', and nitric acid 'O' with 0.05 M D2EHPA in kerosene at 20C (reproduced from Sato et oL 1985).
2. Literature Review and Theo-
However, besides such high concentrations of H2S04not being feasible to work with, the use
of H2S04 is M e r restricted as a sulphur-fiee strip solution must be obtained in order to yield a saleable iron by-product. H m a potential mineral acid to produce sulphur-fiee strip liquors, is expected to be a weak stripping agent, a3 cm be postulated fiom Figure 2.3. This
was recently confirmeci with D2E13PA by Van Weert et a1.(1998), and a similar result is
expected with OPAP. Hence, the interest in this work has focused on the use of HCl as the stripping reagent of choice. Table 2.3 outlines the iron stripping agents employed in various studies. Strong HC1 was
used only in the M2EHPA work. Work w i t h M2EHPA has shown that ambient conditions offer better stripping penormance than higher temperatures (Dernopoulos et aL 1996). In
contrast, DZEHPA and EU2 were tested a t 50C. In terms of stripping kinetics, M2EHPA is very fast requiring 2 minutes to attain practical equilibrium. D2EHPA is problematic, at least with 2 M HzSOc requiring greater than 30 minutes. Both NED and EU2 are acceptable requinng 10 minutes. Table 2.3: Extractant cumparison of i r o n o stripping characteristics @emopoulos et al. 1996, Delmas et d 1996, Lakshmanan et al. 1996). [ E ~ t r a a a n t l - ~ (% ~ 40) 40% M2EHPA 30% D2EHPA 2 M fis04 6 N HCf Stripping agent 50 25 Temperature CC) >30 Contact time (min) 2 >201 75 M a x ~ e build-up ~ ' (g/L) >2 8 No. stages >4 ~ e retention ~ ' (fi) i0 - L ~ e ~ 7 -= w-10 g / ~ 30%, 20% w/wrespective concentdons lO?/ov/oNED - redudve stripping result
'
With respect to the stripping isotherms, despite the large number of studies involving
iron(III) and D2EHPA in the past, unreliable, if not a total absence of HCI stripping
i t h isotherrns were found in the literanire. The McGiWCANMET pilot plant campaign w
M2EEPA @emopoulos et al. 1996) consistently produced a 75 g F ~ ~ +svip / L solution when
a 6 N HCl solution was used as the strip feed. The McCabaThiele analysis of the generated
40% vlo M2EHPA stripping isotherm (not shown) indicates stripping dificulties and an
inability to attain NO0 g/L i r o n o . Spefically, several stages would be needed (8 were tested in piloting) and an unacceptably high amount of iron is retained in the stnpped
organic. This was -10 gR. Kano for an initial loaded organic iron concentration of
-50 g L , when an O/A=1.5operating line was used. Reliable cornparisons of stripping characteristics w i t h other extractants cannot be made as the stripping medium was not HCI.
2J.2 Generic difficulties
It is postulated that based on the above and subsequent information, no single extradant (either from the organophosphoms acid family or from the novel pair, NED and EU2) appears to avoid two generic problems inherent to the extraction of iron@I) h m a strong
ZnS04-H2S04solution, followed by hydrochloric acid stripping, specifically: (i) the transfer
of S O ~andor Cr fkom one phase to the other, and, (ii) the inadequate build-up of iron in the chloride strip solution. uistead, auxiiiary separation and/or concentration (>IO0 fi) concentration technologies will have to be considered to address these problems.
2.1.2 1 ~ 0 : and CT carry-over and possible remedial scrubbing memures
Operating a solvent extraction circuit with different aqueous solution matrices (sulphate versus choride) in the feed and sip phases presents the risk of anion interphase transport and crossontamination via physical entrainment, chernical co-extraction and/or back-extraction.
This is a particularly m c i d issue in the
case of iron(ILl) extraction iom zinc process
solutions as, on the one hand, there is practically zero tolerance in terms of chloride presence in zinc sulphate electrolytes (<100-200 ppm), while on the other hand no sulphur contamination is acceptable in the strip solution if the iron oxide produced downstream is to
be of saleable quality. The understanding of the transport of anions in this application is
h i s d l s for an examination of the specific rnechanisms by which iron is therefore vital. T

extracteci and stripped.
Sulphtzte tramport
Early M2EEPA work had determineci that the relationship between moles of exracted iron versus moles of fiee extractant was 113 (Dernopoulos and Pouskouleli 1989). This finding is consistent with the generally accepted extraction expression for i r o r o as indicated earlier by Equation 2.1. However, upon studying the equilibrium acid concentration effect, findings were not consistent with Equation 2.1 stoichiometry. The relationship of log@,) versus logwS04] gave a dope of 2.14, i.e. the moles of extracted ~ e versus ~ + moles of H2S04 generated, or effectively moles H 'generated, was 112 (Dernopoulos and Pouskouleli 1989).
One possible explanation for this discrepancy is that iron(m) is extracted as a sulphato
complex such as F~HSO?.
To ver@ this postulation, the speciation diagram in Figure 2.4 was constniaed with the aid of an algorithm developed by Filippou et a L (1993). The diagram indicates substantial
presence of F~HSO?' at SOC and pH <0.7 with cationic species distribution following the order F~SO; > F~HSO?' >~ e ~ Aitematively, '. the simultaneous extraction of FeS04+ or
PH Figure 2.4: Iron(m)-sulphate speciation diagram at SOC (0.5 M ~ with algorithm developed by Filippou et uL 1993).
e (constnicted ~ 3
other species cannot be d e d out If the Equation 2.2 mechanism above is true, then
signifiant chernical sulphate cany-over into the stnp solution should ultimately result. This is exactly what was observed during the piloting of the M2EHPA system (Dernopoulos et al.
1996). When no m b b i n g was employed, S O :
reported to the HCI strip solution at values
as high as 55 glL. Saubbing the loaded organic with (NtthSO1 reduced sulphate carry-over to the strip solution down to -12 g/L. Cany-over data for this and other systems is given in Table 2.4. D2EHPA was f m d to strip at 1:1 molar quantities of iron(m) and sulphate indicating significant sulphate CO-extraction. Other possible sulfur carry-over mechanisms
may exist such as the extraction of &SO4 via the formation of w/o microemulsions (or
reverse micelles) with or without the cm-action of the long-chain alcohol modifier. NED
extracts acid fiom non-preneutralized aqueous feed (Lakshmanan et al. 1996). Sulphatdacid
co-ex~action is anticipated for EU2 as well. Table 2.4: Evidence of sulphate and chioride carry-over (Dernopoulos et al. 1996, Van Weert et al. 1998, Lakshrnanan et al. 1996).
[Extractant]-,
phue (% V/O)
Sulphate
Chloride
0 0 h D2EHPA 40% NED 40% MZEHPA 1 1:1 F~~'/sO? Extracts HiSOd 55
(strip solution)
15% EU2 N/A

N/A
22 g/L(raffuiate)
(molar basis) N/A
N/ A
In the case ofD2EHPA, the mechanism put fonvard by Islam et. al. (1979) to explain the 2 to
1 [extractant]@e3*], ratio found when i r o n o is extraaed f?om sulphuric acid media (Sato
et al. 1985, Islam et al. 1979) is expressed by Equation 2.3.
Howwer, iron(m) hydrolysis is highly unlikely to be important here because the extraction pH of interest is l e s than 1 and there is an absence of F~(oH)" in Figure 2.4. Mead, a
mechanism similar to that given by Equation 2.2 for M2EHPA is very iikely for D2EHPA
and the other extra-
as weli. Previous investigations have not considered the m f e r of
~ 0 : -ont0 the loaded DZEHPA phase except for Y u and Chen (1989) who postulated the following extraction reaction at high acidities.
2. Liteniture Review and Tneory
Further work is needed to ver@ the exact mechanism of sulphate transport. Work with the novel reagents (Delmas et al. 1996, Lakshrnanan et al. 1996) should include an examination of the above issue, or contamination of the chlonde strip solution will result in failure to meet
the quality specifications for iron oxide production
Chloride bansport
Mechanistically, the stripping of iron(III)-loaded organophosphorus acids is thought to operate in principle as the reverse of the extraction, given in Equation 2.1.
However, in recent research published by Sahu and D a s (1997), it was determined that logD versus Iog[extractant] plots for o n o extrriction by D2EHPA from concentrated chloride solutions (like those used in HCl stripping) give a dope of 2.2. This suggests the formation
of the FeClY2 complex, Le. the involvement of the F~CI" chloro-cornplex. Hence,
evaluation of the respective F~'+-cI-speciation diagram (Figure 2.5) is considered pertinent to this review. According to the diagram, in addition to cationic species ~eCl?+, other noncationic species such as FeCbOand FeCK are present at the high chionde levels in the range of HCI concentrations that are employed in stripping, Le. 4-6 N. It is of interest to note that according to Figure 2.3, back extraction of k o n o occun above 4 N HC1 in the DZEHPA system. Similarly, recall the significant retention of bon (10 gL) in the stripped M2EHPA phase that was observed in isothenns by Demopoulos et al. (1989, 1996). This points again to some back-extraction of iron(III).
During piloting of the M2EHPA system, significant chloride carry-over f?om the strip phase
to the raffinate phase was observed. Up to 22 g/LClreported to the raffinate (Table 2.4) (Demopoulos et al. 1996). T h i s amount of chloride was found to correlate with the amount of unstripped iron(m) at a molar ratio [~1']&@?e'7, equai to 3. This suggests that at high
HCI concentrations, back-extraction of iron in the form of FeC13"occurs. In addition to the
organophosphorus aQd extractant
0, the modifier used
by Demopoulos et al (1989,
1996), tridecanol
@ O H ) , quite possibly d s o contributed to iron back-extraction via
solvation, as illustrated in Equation 2.6.
Figure 2.5: Iron@l) chloide speciation diagram at 20C (10" M ~ Aprahamian and Demopoulos 1995).
e (reproduced ~ 3 fiorn
The use of other rnodifiers or 'synergistic' additives such as TBP (Sahu and Das 1997) or
amines (Yu and Chen 1989, Ismael and Carvalho 1996) is expected to contribute even further
to iron back-extraction and chloride carry-over. The same may be expected for EU2 @elmas
et al. 1996) which is essentially a 'fused amino-phosphoric acid'.
Detailed studies are
required to charactenze the problem of chloride transport and devise a means for its contml.
The simplest way to deal with the problem of sulphate and chloride caq-over is to incorporate scnibbing steps into the solvent extraction flowsheet (Rincipe and Demopoulos
1998). Sulphate -cted
with i r o n o and zinc shouid be effectively scnibbed by a
chloride solution of weak acidity (0.1-0.2 M HCl) but high chloride content, e.g as MgC12 or
2. Literahrre Review and Theory
FeC12. High chlonde concentration is deemed necessary to push the following exchange reaction t o the right.
The s m b solution, also containhg zinc, is subsequently treated with lime to remove sulphate, and hence regenerate it for recycling.
The cleaning of the stripped organic of its chlonde content pnor to its recycling to the extraction stage has been done in the case of M2EHPA w i t h 50 g/L H2S@ @emopoulos et al. 1996). This procedure led to the complete transfer of chloide with ni1 transfer of
i r o n o . The following mechanism is postulated to explain this scrubbing behaviour (Principe and Demopoulos 1998).
The fate of the produced H2SOJHCl scmb solution i s not clear at this point. Ideally, the regeneration of it via the sepmation of HCf by solvent extraction, for example with a tertiary amine (Ashrafizadeh and Demopoulos 1996), or by other means would be the preferred option. Altemaively, lime neutniliation and disposal is an option, although of questionable environmental merit. For both scrubbing operations, multi-stage counter-current circuits will have to be designed.
2 t2 2 Inadequate i r o n o buWup MdpossbIe supplementary concenboiion
The highest i r o n o level in the HCl strip solution has been reported for M2EHPA (75 g/L).
This level, howwer, is not considerd high enough to allow for economic application of pyrohydrolysis. Pyrohydrolysis i s a high temperatwe thermal decomposition (hydrolysis) of metai chlorides which produces the metal oxide and gaseous hydrochloric acid with either tluid-bed or spray roaster reactors. DZEHPA and EU2 results with different stripping media

suggest that lower build-up is expected (Table 2 . 3 ) . and EU2 is low even with reductive
stripping (45 g / L ) . The only extractant/stripping system that produced i r o n o levels well above 100 g/L was the 40% v/o hydroxamic acid (NED) stripped with 30% HzS04-20%
H$04.
An iron@I) concentration as high as 142 g/L was reported (Lakshamanan et al.
1996). However, the use of &S04-H904 as stripping medium does not allow for the
e s t work production of sulphur-fiee femc oxide by downstrearn processing of this liquor. T

with strono HCI is require.
Electto-mskted stripping To date, with HCl as the stripping agent, it appears that an iron chloride concentration step will have to be introduced between stripping and iron oxide production to make the latter an economically and technically viable option. The following options may be considered: (i) a
secondary solvent extradion circuit with TBP; (ii) the use of membrane technology; and, (iii)
electro-assisted stripping. The f3st two of these options is briefly discussed in Principe and Demopoulos (1 998). A discussion of the latter follows. Reductive stripping as a means of facilitating the stripping of iron with HtS04 &om organophosphonis-type extractant systems is well documented. This method is based on the
fact that ferrous iron, in contrast to femc iron, is less extractable. Majima et al. (1985)
proposed the use of SOI to assist stripping of i r o n o fiom DZEHPA solvent with H2S04. Demopoulos and Gefvert (1984) performed stripping under H2 pressure, while more recently, O'Keefe and w-worken (1996) advocated the use of zinc or iron dust ('galvanic stripping'). However, the problems associated with the above chemical reductive stripping methods, such
as the high temperatures and pressures needed (reduction w i t h Hz) or the contamination of
the strip solution with sulphates (reduction with S a ) or zinc (galvanic stripping), make this approach ditficult to implement.
At McGili, a novel process scheme has been conceived involviag electro-reductive stripping
(termeci 'electro-assisted stripping') as opposed to chemical reductive stripping. Electroreduction of FeCl3 to FeC12 is to be done via an extemal loop as opposed to in-wntact with
the loaded organic p b e .
The conceptual flowsheet with this novel stripping method
interposed between stripping and pyrohydrolysis is shown in Figure 2.6. According to this flowsheet, a high concentration of FeClz is maintainecf in the recycled HCI strip solution, the
h i s high FeClz load strength of which is adjusted with HCl recovered in pyrohydrolysis. T
should not only permit the concentration of iron to economically attractive levels (>IO0 g/L),
but conceptually should increase stripping power by enhancing proton activity (Jansz 1983).
In addition, it ensures the technid feasibility of the fluid-bed roaster-type of pyrohydrolysis
process as it works only with FeC12 liquors (Van Weert 1997). Substantial concentrations of FeCb in a feed liquor will cause loss of particle size control in a Buid-bed reactor
pyrohydrolyzer, thereby failing to produce saleable femc oxide.
Steel pickle liquors
presently treated by fluid-bed pyrohydrolyzers (Poy 1996, Peek et al 1996) have a composition similar to that of the anticipated FeC13-FeC12-HCl stnp solutions.
Loaded Organic (2 1 g L ~
k
e ~ 3
EXTRACTION
HCl STRIPPING
5 glL ~ e ~ +
1 NO0 g/LFe,,
Fe(1II) REDUCTION
(II,III)
1-
PYROHYDROLYSIS
1 1
Figure 2.6: Iron@I) electro-reduction step interposed between solvent extraction stripping and pyrohydrolysis.

2.2 DOWNSTREAM. IRON OXlDE PRODUCTION
An m u a 1 production of 38,500 tons of Fe&
is projected for a 200,000 tpy capacity zinc
plant processing concentrate containhg 7% iron. This is compared to the equivalent in jarosite (80,000 tons) which has to be stockpiled. As a reference, a large steel pickle liquor treatment line produces 15,000 tons of F a 0 3 annually (Poy 1996).
2.2.1 Iron pmduct qudity and market
F a & product can be sold in the magnetic industry (where it is used to produce femtes), in
the pigment industry, or in the iron-making industry. Each of these industries has its own
specifications. In t e n s of sue, the markets rank in the order: iron-rnaking > pigment > magnetic (Pape 1998). Although the smallest of the three markets, magnetics is considered
as a growth industry with femte demand rising at a rate of 10-15Ydyear('Pape 1998). Few
spray roaster operations are able to produce pigment puality iron oxide. However, when it
cornes to pigment production or iron-making, the &O3
produced by fluid-bed
pyrohydrolysis is superior due to the better particle size control achieved and the lower chloride content in the final product (Pape 1998; Van Weert 1997). Iron-making industries
pay the sarne price as iron ore for feedaock More iron in hematite than iron ore (70%
versus 60%) gives very clean hematite a selling advantage (Bialko 1998).
2.2.2 Fluidized-bed r o ~ s t e pyrohydrolysis r
Potentiai iron mede prodrrcts
A variety of iron oxide product routes via pyrohydrolysis are to be considered. T h i s is

advisable since direct production of a saleable hematite product specifically may be unrealistic. No effort has yet successfully pyrohydrolyzed FeC13 to low chloride levels in the hematite while at the same tirne achieving high regenerated HCl product concentration (Van Weert 1997).
Other routes include: (i) FeC12*xH20,which is produced either by
crystallization f+om scmb solution or by stnp solution evaporation; this can then be converted to hematite produchg HCl at concentrations greater than the azeotropic level (Van Weert 1997); (ii) by using ZnC12 instead of or in combination with FeC12 to enhance proton
activity, zinc is eliminated fiom the bed product via the scrub solution which is recycled to
the process (Peek et a L 1995); (ii) producing a saleable calcine (via Q technology in the
fonn of MgU-Fea) in the pyrohydrolyzer (with no necessary reduction) is atraaive as the
M g C a feed is available at low cost; this only works with the fluid-bed roaster (Van Weert
1997).
Contamjnarrt issues
The femte industry will not tolerate >2 ppm zinc while the iron industry will not tolerate
>200 ppm zinc in their uon feedstock. However, steel pickie liquors containino 5-20 @
zinc routine1y process very well by fluid-bed pyrohydrolysis (Peek 1998). Researchers should be more concemeci with strip solution Na, Mg, and Ca constituents which would not l a v e the pyrohydrolyzer, unlike zinc which does above 1005K, but instead report to the oxide product as chlorides, possibly affecting bed performance and clearly compromising produa quality (Peek 1998). Although chlotide content in the iron oxide product is not known to depend on the concentration of chlonde in the feed, chloride contamination is still a challenge and of greater concern than zinc (Peek 1998).
2 . 2 . 3 Spray roaster pyrohydrolysis

Although spray roasting can more tolerably process iron(m)-containing solutions, o n o content must still be low to ensure good particle size distribution control. ahenvise product quality also d e r s here (Pape 1998). Spray roasting requires a minimum of 6 . 7 % problems with the intended strip solution (Bialko 1998). iron and a
maximum 8-9% wlw HCI in its feed solution, which appears to pose no cumpatibility
3. Emerimental 3. ExPERIM-ErnAL
3.1 REAGENTS
Analytical grade inorganic chemicals were used in al1 the experiments, and al1 solutions were prepared with de-ionized water. The synthetic aqueous feed and strip feed solutions were
prepared with the chemicals at the target concentrations listed in Table 3.1. The standard
aqueous feed composition selected approximates the hot acid leach overflow strearn of an
RLE process: 25 g/Li r o n o as Fa(SO&, 90 g/L zinc as ZnS04, and 50 g/L HzSOd.
Table 3.1 : Inorganic reagents used in experimental work
Solution or 1 Compound Application Aqueous Feed I.on(III) sulphate pentahydrate (97% w/w) 1 Zinc sulphate heptahydrate (>99% w/w) ~ u l ~ h u r&id i c (95-98% w/w) 'trace metal' Strip Feed Hydrochloric acid (3 5.38% w/w)
-
Supplier
Aldrich A&C Fisher Fisher Aldrich Aldrich I r o n o chloride hexahydrate (98% w/w) Free Acid Magnesium sulphate heptahydrate(>98% w/w) Aldrich BDH Titration Disodium ethylenediarnine tetracetic acid Anachernia Sodium hydroxide standard (1 N) Potassium biphthalate standard (99.990h w/w)Anachernia Aldrich Potassium dichromate volumetric standard Total Iron 'trace met al' Fisher Titration Hydrochlork acid (3 5-38% w/w) Stannous chloride dihydrate (98.4% wlw) Mallinckrodt Fisher Mercuric Chlonde (99.6% w/w) Fisher Ortho-phosphoric acid (85% w/w) Fisher Sulphuric acid (95-98% wlw) Sodium di~henviamine sulfonate indicator Anachernia standardized with potassium biphthalate * - for H2S04-&PO4bufEer preparation
Prepared Concentration 25 g/L~ e j + 90 g/L Zn2' 50 &SOI 4-8 N HC1 30-70 g/L ~e:
Al1 three extractants under shidy, OPAP, D2EHPA, and MZEHPA, were of industrial grade, received fiom theu respective suppliers as recent 1997 products. Unlike D2EHPA and
M2EHPA, which are in liquid fom, OPAP is a semi-solid at arnbient conditions having a
melting point of 6SC. OPAP also differs in that it does not consist of one predominant
moleailar form, but instead is essentially an equimolar mixture of mono- and di-dIql OPAP
esters. The molecular weight of OPAP was estimated to be 401 glmol as determined by acid-
base titrations of solid samples performed as part of the experimental work and descnbed in
Section 3.3.1. T h i s value is only an approximation as the relative proportion of mono- and di-esters varied with different samples because the starting OPAP solid was not homogeneous in composition. The following composition ranges, on a molar basiq were detennined by titration analysis: 50-54% mono-OPAP; 4640% di-OPAP. Tndecanol(20%
VIV or 0.84 F) and kerosene were used as the modifier and diluent, respectively, for al1
extractant solution preparations which were at 0.95 F11.25 F concentrations (Table 3.2). Acetone was used as a solvent in the titrations of d l freshly prepared extractant solutions, for concentmiion adjustment purposes, as well as al1 OPAP solid samples (see Section 3.3.1). Table 3.2: Organic reagents used in expenmental work.
Matenal
Compound
Prepared Concentratior Albright & Wilson 0.95 F OPAP
Supplier
batch 2: 89.5%; si. 1.O8 (25OC) Modifier Tridemol, EXXAL-13(CIJI&Hisomers) Diluent Kerosene, commercial grade Solvent Acetone (>99.5% wlw)
Hoechst
Albright & Wilson EXXON Fisher Anachernia
Figure 3.1 shows the structural formula of each extractant. Al1 three are organophosphoric
acids. It is worth noting that OPAP clearly has the greater shed substituent group (14>R3)
which gives it the highest molecular weight of the three extractants.
Figure 3.1: Sbuctud formulae of D2EHPA (Rl=Rz=&), M2EHPA @1=R3; Rz=H), and OPAP (50% Ri=R2=R4 and 50% R i = & , R2=H, molar basis). 3 . 2 EXTRACTANT PREPARATION 3 . 2 . 1 OPAP preparation Approximately 780 g of the semi-solid OPAP extractant was melted in a covered beaker that
was immersed in a heated water bath. When completely melted, 762 g of the hot OPAP
liquid was mixed with 400 r d . tridecanol until the hot solution appeared clear. This was
done before adding any kerosene to ensure that no precipitation would occur. Unlike tridecanol, kerosene is partially immiscible in OPAP alone. Kerosene was then added to give a total volume of 2 L. The solution was then shaken and ailowed to stand.
Since the original semi-solid is not homogeneous in concentration, extractant concentration
adjustment was necessary for the fieshly made organic solutions. As the extractant itself is
an acid, an acid-base titration with 0.1 N NaOH titrant using an automatic titrator diceci, as
describeci in Section 3.3.1.

3.2.2 DZEHPA and M2EEPA preparation
Since D2EHPA and M2EHPA exia as liquids at room temperature, no heating was necessary in their respective preparations. Consequently, the same solution preparation as above for
OPAP was foiiowed except that a measured volume, not masq of the extractant was added to
the modifier and diluent.
3 . 2 . 3 Conditioning of prepared extractants
These extractants, being of industrial grade, contained soluble impurities which had to be
removed prior to experimental work. Table 3.3 lists the synthesis by-products declared by
the suppliers of the four extractant batches received.
Table 3.3 : Impurities present in received extractants as declared by suppliers.
Extractant Pril2EHPA (Hoechst batch) (Albright & Wilson batch) D2EHPA
OPAP
Im~urities 5% DZEHPA., 8% H904 8.5% D2EHPA 2.5% MZEHPA <2% anhvdride of mono-OPAP
1
+
The washing procedure adopted, referred to as 'conditioning', was based on work by Molnar
et al. 1989 in their study of M2EHPA This consisted of contacthg a single prepared
extractant solution with consecutive contacts of fresh 50 g L & S 0 4 at SOC (AfO=l.O) until
an apparent solubility baseline w a s attained. Section 4.1.1.1 experimental work determined

the required number of contaas to main this baseline for each extractant. Following
washing, the extractants were either centrifugecl or allowed to stand in a large separatory funnel, time permitting, for complete removal of the aqueous phase prior to loading or stripping tests.
3 . 3 ANALYTICAL METHODS
3 . 3 . 1 Free acid titrations
~ For al1 free acid titrations, a RADIOMETER COPENHAGEN T I T R A L A B ~90
programmable autotitraior was used. Its accessories include: the TIM 900 Titration Manager
(8-line LCD) interfriced to a dot matrix pinter, the ABU 900 high precision Autoburette
System (20 mL burette size); a SAM 7 sample stand; and a glass pH electrode. As well for
al1 fkee acid titrations, a titrant of 0.1 N NaOH was used.

3.3.L 1 Extractant concuitration @ustment offieshIy prepmed owmic solutions
The method described by Mihaylov (1991) was adopted for the acid extractant analysis for
concentration adjustment purposes of the fieshly prepared organic solutions. The same
method could be appiied to al1 three extractant preparations in a non-discriminatory manner.
Solid OPAP starting material was also analyzed by this method.

In a 150 mL beaker equipped with stirring bar, typically a 1.00 rnL aliquot of extractant
solution (or 4 . 4 5 g OPAP starting solid) vras mixed with 100 rnL reagent gracie acetone. Then, 25 mL of distillai water was added. Al1 extractant solutions were titrated at least to
the first inflection point. The first inflection point volume (VI) gave the overall extractant
concentration, e.g. the sum of both f o m of OPAP. This is because the first dissociable protons of d l esters present are neutralized preferentially by the titrant before the second dissociable protons of any existing mono-alkyl esters. In the case of OPAP analysis, the
was attained. The titration was continued until the second inflection point volume (V2)
expressions (V2-VI)and Vp(V2-VI) were used to calculate the rnolar fiactions of monoOPAP and di-OPAP, respectively.
3.3.1.2 Free acid determinations in expm0mentdqueous $amples
The aqueous f i e acid (H2S04 or HCI) determinations followed were adaptations of the method by Rolia and Dutrizac (1984) which employs M~EDTA"reagent to prevent metd hydrolysis, by formation of stable metal complexes, while acid is completely neutralized. Sulphate-based sarnples from aqueous feed and ranate solutions were titrated to a set
endpoint pH while chloride-based samples of strip solutions were titrated by inflection point analysis. Standardkation and calibration procedures were developed and applied. The modified procedure is given in Appendix A 3 . 3 . 2 Total I r o n o titntions
An analytical redox titration method commoniy used in industry (ASRII 1969) was used to
determine total iron in the aqueous sample solutions. With respect to the sample matri%this
method is non-discriminatory, capable of analyzing either sulpbate or chloride-based samples.
The apparatus used wmpnsed a 50 m .g l a s buret, 150 mL beaker, magnetic stimng bar,
and stimng plate. A 1.00 mL aliquot was added to the beaker after which a sequence of
various reagents, as listed in Table 3.1, was added. This preparation sequence began with the addition of concentrated HCl to give a constant acid chloride background concentration. Subsequently, SnC12 was added to reduce any i r o n o content completely to iron@). Then, HgClz was added to oxidize any excess SnC12, while being weactive with any ironw). The
organic iron content was determined by difference in aqueous phase results.

3.3.3 Organic sample analysis
Udike total iron, 2n2> S (as ~ 0 4 3 and , Cl- content in the organic samples were analyzed
directly, because calculations using changes in aqueous phase composition, as was done with
iron, were unreliable for these elements. This is because the changes in aqueous sample compositions were relatively small, arguably within the experimental error of analysis of the and sulphate starting aqueous solutions, which contained very high levels of zinc (90 g/L)
(-250 g/L) in raffinates and chloride (M40 g/L)in strip solutions. Therefore, organic
samples were individually scnibbed. The resulting scrub liquors were then analyzed by Indudively Coupled Plasma Spectroscopy (ICP) for zinc and sulfur or by Ion Chrornatography (IC) for chloride.
Scrubbing of zinc and sulphate from loaded organic samples was h e d out at 20C and
O/A=0.50. The equipment consisted of 35 rnL glass vials with ~eflon@ lined caps and a
centrifuge. A 1.00 mL aliquot of loaded organic was diluted to 5 mL with a 1:4 tndecanolkerosene solution. Five consecutive contacts of 9.9 mL fiesh 30 g/L (0.82 M) HCl volumes
were made with the same organic. For each contact, the glas via1 was hand-shaken for 2 minutes then centrifuged. Al1 five scrub liquors were cornbined and diluted to 50 mL. The
scnibbed organic was then contacted with 10 mL of 6 N HCl as a separate 'check' for mmplete removal. Scmbbing of chloride fkom stripped organic samples involved a procedure similar to that above for zinc and sulphate. Major differences include: (i) samples were stripped organic, not loaded as above; (ii) three consecutive contacts with 10 rnL of 50 g/L (0.5 M) HzS04
were made since two contacts suficed with M2EHPA according to Dernopoulos et al.
(1996); (iii) the stripped organic phase was contacted w i t h another contact of 10 rnL of
50 gR.(0.5 M) HzSO~ a s a separate 'check'.
3. Experimental
3.3.4 hductively coupled plasma spectroscopy ('KT)
A Thermo Jarre1 Ash 'Trace Scan' axial ICP was used to analyze the wash liquors for
phosphorus and the sarnple s m b liquors for zinc and sulfur. Joint zinc-sulfr standards of O,
1, 5, 1 0 , 20, and 40 ppm and phosphorus standards of 5, 10, 20, and 75 ppm were required,
containing matrices similar to the corresponding experimental samples.

33.5 Ion chromatography (IC)
A DIONEX DX-100Ion Chromatograph was used to analyze for Cl- in sample scmb liquors.
Its accessories included: IONPAC ASl2A 4 mm chromatographie column; IONPAC ASRS-1

4 mm anion self-regenerating suppressor; conductivity detector; and cornputer interface.
Chionde standards containing 0 , 0.5,1, 5, and 1 0 pprn were used, each containing 500 ppm
HzSO4 as the background matrix.

3.4 EXPERIMENTAL PROCEDURES AND SET-UP
This section initially describes dl the tests conducted. Details of the experimental apparatus then follow.
3.4.1 Extractant solubility and stability tests
3.4.1.1 Iktractant condilioning attd solubility in pure H
m and HCI sokutions
Conditioning tests consisted of contacting a single prepared extractant solution with aliquots of fiesh 50 g/L &SOI at 50C, A/O=1.0(organic continuous), and 900 rpm agitation for 10 minutes per contact. Nine consecutive contacts were made with the fiesh acid aliquots. Wash liquor samples were centrifuged and analyzed for residual phosphorus. This conditioning procedure functioned additionally as a test of the solubility of each extractant in
pure K2S04 solution. The same applied to HCl solution tests with the exceptions that the
temperature was 20C and that 6 N HCI solution was used to simulate the stripping medium
of interest. The extractant solutions from H2S04 conditioning were the starting organic phases tested w i t h HCl solution.
3.4. L2 &tractant solubiliiy in aqueousfeed and snip solutions
The extractant solubilities in aqueous metal-salt solutions were compared by subjecting

freshly prepared and conditioned OPAP and DZEHPA solutions to single 2-hour contacts
either under loading or stripping conditions. Loading involved contacting the organic with
aqueous feed at 50C, AIO=1.0 (organic continuous), and 1600 rpm agitation for 2 hours.
The metal salt source during loading was the standard aqueous feed of HAL composition (Table 3.1). For the stripping tests, the extraaants were initially loaded at 50C with 2
contacts of standard aqueous feed (A/O=1.0, organic continuous), each for 20-25 minutes contact time. The loaded organic was then contacted with 6 N HCI strip feed at 20C,
O/A=1.0 (organic continuaus), and 1000 rpm agitation for 2 hours. Metai salt presence
consistai of iron(III) as FeCI3 that was stripped fiom OPAP and DZEHPA at levels of 10 and
14 g/Li r o n o , respectively. Emulsion sampling was done at 10, 20, 30, 60, and 120
minutes for al1 tests. The emulsions were centrifuged and the aqueous portions analyzed for residual phosphorus content.
3.4.1.3 Long-tenn degrnAnn'on tests
Degradation tests required the use of fieshly prepared OPAP and D2EHPA which were conditioned and centrifuged to remove any entrained aqueous phase prior to contacting with aqueous feed (standard) or strip solutions. The strip solution wntained 6 N HCl and 40 g/L
i r o n o as FeCb. Each of 8 possible combinations of operating parameters were tested in different shake flasks in which the extractant (unloaded OPAP or D 2 m A ) and the aqueous medium (aqueous feed or stnp solution) were rnixed at a temperature of either 20C or 50C.
The extractants used for the simulated stripping conditions were not pre-loaded as this would
have introduced co-extracteci sulphate ions to this evaluation which would have complicated
the analysis of the results. The iron(m) present in the strip feed was in excess of the
stoichiornetric required amount, being distributed arnong the two phases in equilibrium minutes after the start of 'degradation' testing. The phases were rnixed continuously with a wrist-action shaker. The shaking was achially 'semi-continuous' as 6-hour rest intervals were allowed every 48 houn in order to avoid shaker-motor strain. Aqueous and organic samples were taken respectively every 4 and 8 days, each sample being replaced wiih wnditioned Eesh material. Aqueous samples were analyzed for residual phosphorus content
as a means of monitoring degradation.
3.4.2 Extraction tests
3 . 4 . 2 1 I%hction Rindcs tests

OPAP extraction kinetics tests involved contacting the conditioned extractant with aqueous
feed solution at 20C or 50C, A/=2.0(aqueous continuous), and 1350 rpm agitation for 15
minutes total contact time. The aqueous feed solutions cantained initial acid concentrations of 12.5 fi 25
a, 50 g/L, and 75 g/L H2SOc Emulsion samples were pipetted at 2, 5, 10,
and 15 minutes. Raffinates were titrated for fiee acid and total iron content. Loaded organic samples were stripped with 30 glL, HCl generating scrub liquors which were analyzed for
zinc and sulphur. In contrast, D2EHPA tests were agitated at 1050 rpm and each required
additional emulsion samples at 20 and 30 minutes, i.e. 30 minutes total contact time.
D2EHPA kinetics tests only involved 12.5 gR.and 50 g L HzS04 aqueous feeds. For al1 tests
conducteci, the agitation speeds opted for were those which provided optimal mixing, which ensured chemical reaction controlled reaction kinetics. Typically, the speeds used for tests
w i t h OPAP and D2EHPA were different due to the disparity in organic phase viscosities.
3 . 4 . 2 2 Extraction isoihentts
OPAP extraction isotherms involved contacting the conditioned extractant w i t h aqueous feed
solution at 20C or 50C and 1000-1800 rpm agitation for 20-30 minutes total contact time.
nie O/A phase ratios were O. 10, 0.14, 0.25, 0.50.0.75,1.O, 4.0, 7.0, and 10. Except for O/A
phase ratios 4.0-10 and sometimes 1.0, mixing was conduaed aqueous continuous. A second ~eflon@ impeller was used on the agitator shaft for O/A ratios 4.0-10 to ensure adequate
mixing. The minor phase volume used at phase ratio extremes (O/A=. 1, 10) was 12 mL in al1 isotherms (extraction or stripping). The aqueous feeds contained initial acid concentrations of 15 glL or 50 g/LHzS04. Samples were taken either as emulsions, which were then centrifbged, or draine- ftom the mix tank through a stopcock upon phase
separation. Raninates were titrated for 6 e e acid and total iron content. Only one DZEHPA test was performed, operating at SOC with 50 g/LH2SQaqueous feed for dl contacts.
3.4.3 Stripping tests
3.43.1 Sbipping Rinetics tests
Stripping kinetics tests were paformed with conditioned OPAP and DZEHPA which had
been pre-loaded by two conseaitive contacts with standard apueous feed solutions at 50C,
AIO=1.0 (organic continuous), and 20-25 minutes per contact. The uon(m)-loaded OPAP
was contacted with strong hydrochioric acid solution at 20C, O/A=.50 (aqueous continuous), and 1300 rpm agitation for 15 minutes total contact t i m e . The strippant solutions contained initiai acid concentrations of 4 N,6 N,or 8 N HCl and 0-70 g/LFe@) as
Fe&
Emulsion samples were pipetted at 2, 5, 10, and 15 minutes and centrifiged. Strip
solutions were titrated for total iron content. D2EHPA tests were performed similarly except that sampling occurred at 5, 10, 15,20, and 30 minutes, i.e. 30 minutes total contact time.
3.4.3.2 Stripping isotherms
Stripping isotherms were perfomed with conditioned OPAP and D2EHPA which had been pre-loaded by two consecutive contacts with standard aqueous feed solutions at 50C,
A/O=1.0 (organic continuous), and 20-25 minutes per contact. The irono-loaded OPAP
was contacted with 6 N HCI-FeC12 (0-70 g L ~
e or ~ 'moderate 3 strength' strip feed (3.38 N
HCI-58.5 g/LF m 9 . 7 g , ' F a ) solutions at 20C, 1300-1800 rpm agitation, and 20-30
minutes total contact time. The O/A phase ratios were the same as those for the extraction
isothenns. Except for O/A phase ratios 1.0-10, mking was conduaed aqueous continuous. A second ~eflon@ impeller was used on the agitator shaf for O1A phase ratios 4.0-10.
Samples were taken either as emulsions, which were centrifged, or drained fiom the rnix
tank through the stopcock upon phase separation. Strip solutions were titrated for total iron
content. Except for a lower required agitation of 1000-1350 rpm, DZEHPA test conditions were identical to those of OPAP.
3.4.4 ExpeRmentril set-ups
3* 4*4 1 Long-te~tt degradation tesis
Long-term degradation shake-out tests were perfomed with a BURREU Wrist-action
Shaker Mode1 75. This apparatus could accommodate 12 sarnples simultaneously. Samples
of the o r p i c and aqueous phases were shaken in 500 mL glass-stopperd Erlenrneyer flasks
to study acid and temperature effects on the degradation of D2EHPA and OPAP under long-
term simulaed loading and stripping conditions. The contents of 6 flasks were maintained at 50C by the use of extemal1y wrapped THERMOLYNE BRISKHEAT flexible electric heating tape, 52 Wf12O V silicone mbber-lined with fibreglass cloth insulation covering.
The heating tapes were connected in parallel to an 1875 W powerbar, STACO 0-140 V
Variac variable transformer, and 120 V outlet series.

3.4.4.2 Solilbility, extractih, and StBpping tests
Al1 solubility, extraction, and stripping tests were conducted in 210 rnL operating capacity square pyrexe tanks. Figure 3.2 illustrates the general configuration of the square tank with
additional design detail in Table 3.4. Operation at 50C required pre-heating of each phase in
different graduateci cylinders which were immersed in water b a h . Following transfer to the
reaaion tank the reaaion temperature was maintained by regulated exposure to an extemal
infiared heat lamp.
DC motored stirrer
0-
outlet
impeller shaft
Control Box
impeller
drain
Figure 3.2: Schematic of experimental apparatus for solubility, extraction, and stripping tests.
Table 3.4 lists the equipment used. DAYTON overhead DC stirrer motors and extemal
speed cuntrols were used to drive the impeller. To ensure an entirely inert apparatus, the
agitation shaft was made fkom titaaium and the impellen and tank cuvers were machined
~eflon? The square tank apparatus equipped with pumpmix design-type impellers was
chosen as it simulates the fluid dynarnics in an SX mixer-settler mixing chamber. As in industry, this apparatus does not require baffles as the square tank configuration sufficiently promotes its own turbulence. A schematic of the impeller design is shown in Figure 3.3. The wmplete apparatus is shown in Figure 3.4. Table 3.4: Major equipment used in solubility, extraction, and stripping tests.
Square Pyrexa tanks
glass blown using: Wilmad Glass # WS 16Oh
Cylindrical
PyrexQP tanks (1.5 L, 2 L)
DC overhead stirrer
1 1
Reactor cuvers Agitation shaAs & im~el lers IR heat lamp assembly
60*60180mm id 210 mL operating capacity glas drain; no baffling 4 mm ~eflon@ stoocock assemblv 1 1 . P 16 cm id (1 L op. cap. tank) glass blown using: 14.5*16 cm id (2 L op. cap. tank) pyrexe cylinder tubes 3 bafflesitank (wall indentations) drain and stopcock same as above 1/27 HP;90 V DC; 5 A; DAYTON mode1 4 2 142 0-1800 rpm DAYTON mode1 42527E 1150-116 HP;90 V DC;115 V Sized for each tank machined ~eflon@ sheet machined Ti & ~eflon@ 7 mm diam. Ti shafts impellen 25,32 mm diam. ~eflon@ rods 175 W heat bulb with brass base PHIWlJPS IR175CPAR bulb 1 ceramic socket; 140 V Variac
-
side view
bottom view
Figure 3.3 : Schematic of pump-mix design-type impeller.

3.4.13 Erfracta conditioning and p r e - l d n g prepmations
Extractant conditioning and pre-loading (for stripping tests) always involved bulk quantities.
These treatments were done in 1L and 2L operating capacity cylindrical pyrexe tanks, each
equipped with the same overhead agitation equipment as mentioned above. These tanks
required larger impellers and included baffling, in contrast to the smaller tanks (Table 3.4).
Figure 3.4: SX mixer apparatus.
4. Results and Discussion

4. RESULTS AND DISCUSSION
4.1 IE'XTRACTANT SOLUBlLITY AND STABlZiITY
Since there is zero tolerance for residual organics in downstream zinc electrowinning, an examination is needecl to quantiq and characterize the origin of organic transfer to aqueous phases. Specifically, the eEect of acid medium, metal-salt presence, and temperature on two major causes of organic transfer, extractant solubility and degradation, were studied. Organic entrainment was not considered.
S Abilty
Acid washing comparing OPAP, DZEHPq and M2FiHPA was performed to establish the extnictants' solubility in pure acid solutions, H2S04and HC1. Results with sulphuric acid solution were used to define the reguired conditioning of fresh extractant solutions prior to loading and stripping. Specifically, a solubility baseline was established for each extractant at which both effective H2S04 washing of impurities was accomplished and residual phosphorus analysis of wash liquors reflected a constant extractant sclubiiity. With this
baseline, the number of contacts necessary to adequately condition each extractant was determined and used as a standard procedure. contai~ng queous feed and strip solutions.
Apart f?om conditioning information,
solubility data in both acid solutions providecl insight into extractant solubilities in metal-
Tests were then performed under loading and stripping conditions, comparing OPAP and
DZEHPA in order to determine the impact of metal salts on solubility in the presence of
either acid solution. Specifically, the kinetics of solubilization of each extractant under single contact simulated batch conditions was examineci.
Stabiliq
Long-term degraation tests were perfonned on OPAP,D2EHPq and M2EHPA in contact
with aqueous feed and strip solutions at ambient and elevated temperatures. The obtained
resuits were interpreted by making reference to previous solubility findings, solution matrix differences, and certain mechanistic information fiom the literature.

4.1.1 Fresh extractant conditioning and solubility
Conditionhg was necessary because the extractants of interest contained aqueous-soluble synthesis by-products that had to be removed prior to loading. Without prior removai, these impunties could potentiaily contaminate aqueous strearns andfor form aqueous soluble iron(m) complexes that d d distort loading and stripping results.
Aqueous stream
contamination in the form of organics would likely translate into an unacceptable compromise in downstream zinc electrowinning current efficiency. Zt is for these reasons that a washing procedure was adopted here, previously developed by Molnar et al. (1989).
4.1.1.1 MQCiarttconditioning and soiubility in purc HSO4 and HCI soIutions
A total of 29.45 g P L was present in 0.95 F of each extractant. Using units of ppm residual
phosphorus is an effective meanire as it reflects extradant dissolution, and stability, on a molar basis. It should be noted, of course, that this does not reflect relative total organic content, e.g OPAP is compriseci of 30% more organic content, by weight, than DZEHPA.
Sulpkuric acid conairioning
For the phase disengagernent of H2S04 conditioning contacts, OPAP required <2 minutes
and 0 . 5 minutes for primary and secondary breaks, respectively. Wash liquors fiom the
fust two contacts tended to be cloudy with what appeared to be fine white suspended emulsion droplets. Samples were consequently centrifugeci so that analysis results would not consider entrainment. This aqueous phase cloudiness was not evident in later contacts for either extractant. The OPAP phase became milky white (opaque), but reverted to transparent yellow in later contacts. M2EHPA batches required 1.5-2.5 minutes and 2.5-4 minutes for primary and secondary breaks, respectively. Otherwise, MZEHPA behaviour was similar to that of OPAP. In contrast, D2EHPA exhibited clear disengagement of both phases and rapid separation at al1 contacts rquiring only 40 seconds and 60-75 seconds for primary and
secondaxy breaks, respectively.
s aqueous solubility of d l 3 extnictants in terms of number of contacts. Figure 4.1 s h ~ w the
Figure 4.2 replots the OPAP and M2EHPA r d t s of Figure 4.1, comparing them in t e m of acid medium.
4. ResuIts and Discussion
nu,
1500
4 5 6 7 8 EJo. Fresh 0 . M H$W4 Cantads
N o .Fresh 6NHCl Contacts
Figure 4.1: Conditioning of fiesh extractants (0.95 F; NO= 1.O; 10 minutes/contact): (a) 50 g/L HzSQ at 50C; (b) 6 N HCl at 20C.
Figure 4.2: Conditioning of fie& extractants (0.95 F;AI-1 (a) OPAP; @) D2EHPA
.O; 10 minutedcontact):
Table 4.1 shows the total losses after seven contacts for each of the three extractants (which
were originally 0.95 F). For this calculation, it was assumed that the same concentration of
extractaat correspondhg
to its baseline solubility reported as losses dong with the soluble
impurities at each of the seven contacts. Seven contacts of HzSCh were required to remove
soluble impurities fiom OPAP and M2EHPA, i.e. attaining the baseline or normal solubility of the extractant in 50 g/L H2S04. The DZEHPA batch was very pure requinng only 1 contact to attain its baseline, acnimulating a total loss of only 261 ppm or 0.9%. However, very high initial solubility losses are evident for OPAP (5%) and M2EHPA (29%). Previous work @emopoulos et al. 1996) with a different batch of WEZIPA showed a similarly high solubility loss (20%) as found here. T h e impwity content declared by suppliers in the
original extractants as teceived is Qiven in Table 3 . 3 . The 8% H3P04content (of unreaced
starting synthesis material) is undoubtedly the major source of M2-A accurate, this loss represents 5.46 g/LP (64% of the total 8.47
initial losses. If
a P lost) which back-
calculates to a more representative 0.84 F (87.8%) overall active M2EHPA than the value given in Table 4.1. OPAP ester anhydride (-2.5%) and partial contribution by mono-allcyl
OPAP were both likely responsible for high initial losses by OPAP.
Table 4.1: Cumulative losses after 7 contacts with fresh 50 g/L H2S04 (50C; NO=1 .O;1O minutedcontact).
Fresh Extradant (0.95 F) MEHPA OPAP D2EHPA
Phosphorus Ioss (gL)

8.47 1.55 0.26
Active Extractant 0.68F (71.0%) 0.90F (95.0%) 0.94F (99.1%)
Table 4.2 shows extractant solubility in pure H2SQ solution after each contact for an
evidently purer MZEHPA available on the market. It does not exhibit such a high initial solubility loss, having a lower baseline solubility (215 pprn P versus 295 ppm P) and minimal cumulative losses (0.06% P lost or 0.948 F active M2EHPA). Cupertino et. al (1994) reporteci that Zeneca has developed DS 5834, a M2EHPA derivative, that exhibits improved solubility and stability characteristics. However, no quantitative data was available. Table 4.2: Sulphuric acid conditioning of Albright & Wilson M2EHPA (0.95 F) batch.
Contact Number (fiesh 50 g/L H2S04at 50C)

1
[Pl,
(p pm) 28 1
Solubility ih hy&ochIoric acid
Tests with HCl solution were conducted to simulate stripping without the presence of metal salts. The chosen mixing temperature was 20C as ambient temperature was found to be associated with optimal M2EHPA stripping results @emopoulos et al. 1996). The same is anticipated for DZEHPA and OPAP. These tests also attempted to veriQ if the higher transfer of M2EHPA to the strip solution relative to raffinates, as found in pilot work (Dernopoulos et al. 1996). is attributed to ineffective prior conditioning with H2S04.
The phase disengagement of OPAP in HCI solution was similar to that observed with
sulphuric acid conditioning in both phases, becoming clear in later contacts. The phases required 4 minutes and 10-11 minutes for primary and secondary breaks to occur, respectively. D2EHPA had similar phase separation times, 3 minutes and 8-13 minutes, respectively. However, D2EHPA remained cloudy white throughout the 9 contacts while al1 the wash liquors were always clear.
In wntrast, M2EHPA phases were both clear,
undergoing primary and secondary breaks in 20 seconds and 2 minutes, respectively. HCI treatment requinng longer times for OPAP or D2EHPA phase separation is not a concern as
this will not be the actud conditioning treatment for fiesh extractant solutions. However, this rnay be an indication of long phase sepanition times in achial stripping tests.
As can be seen in Figures 4.1 and 4.2, littie organic transferred from OPAP or DZEHPA
reported to the aqueous HCI solution as compared w i t h H2S04 conditioning results. The HCI washing baseline was attained afker only the fint contact for al1 three emctants. The data
also indicate that there is no appreciable solubility loss confirming that prior conditioning
with H2S04removed al1 aqueous-soluble impurities effective1y.
Solubility baselines achieved in each ucid medium
The solubility baseline determines the number of contacts needed as well as the losses to expea o r n washing. The latter applies in the case of H2S04. T a b l e 4.3 lists the solubility baseline levels (in ppm P) which follow the order: M2EHPA > OPAP > D2EHPA for both acids.
4. Resufts and Discussion
Table 4.3: Extractant baseline of aqueous solubilities dunng acid washing.

. -
Extractant (O. 95 F) 0.5 M H2S04(50C) 6 N HCI (20C)
M2EHPA 300 190
Baseline Solubility (ppm P) OPAP 30 10
D2EHPA
20
In tenns of extractant solubility on a molar basiq it can be said that OPAP solubility
compares reasonably with that of D2EHP.4 Due !O lower relative hydrophobicity, it is the
presence of the more soluble mono-allcyl OPAP ester component which raises the OPAP baseline above that of D2EHPA in both acids. OPAP and D2EHPA are more soluble in
0.5 M H2S04at 50C than 6 N HCI at 20C. Recd that hlZEHPA pilot work @emopoulos
et al. 1996) yielded higher organic transfer to strip solutions (80 ppm P) versus raffinates
(12 pprn P). It is therefore concluded that the order of M2EHPA pilot plant organic transfer (i.e. strip solutions >> raffinates) is not due mainly to the relative solubilities in pure acid solutions. This calls for the study of time and metal-salt presence effeds on extractant solubility.
4.1.1.2 Extractani solubility in aqueousfeed and sinp solutions
Figure 4.3 shows the kinetics of solubilization of the freshly conditioned extractants in single contacts under either loading or stripping conditions with metai salts present. D2EHPA appears to have an immediate baseline solubility while OPAP solubility steadily increases in either medium throughout the 2-hour contact. Under loading conditions, OPAP solubility increased from a total of 1 ppm P in the nifinate phase frorn O to 30 minutes, to 3 and 5 pprn
at 1 and 2 hours respectively. DZEHPA solubility was wnstantly below 0.2 pprn P. In
stripping OPAP, a total of 12 pprn P reported to the raffinate phase in less than 10 minutes, inaeasing only to 13 pprn P after 1 hour. DZEHPA solubility during stripping was constant throughout the 2-hour period at 16 pprn P, the highest result of these tests.
1 +OPAP Ooading, 50C) 1 B D 2 E H . A (ioading, 50C)
+OPAP (stripping, 20C)

+DZEHPA
1 (stripping, 20C) 1
20
40
60
80
1O 0
120
Time (min)
Figure 4.3: Extractant solubility kinetics of OPAP and DPEHPA (0.95F) under loading and stripping conditions. Table 4.4 lists the final residual phosphorus concentrations after 2 hours for the same tests. Compared to D2EHPA, OPAP clearly exhibited higher solubility during loading but lower solubility during stripping. When cornparhg these OPAP and DZEHPA values to the corresponding baseline solubility results, in pure acid solution kom Section 4.1.1.1 (Table
4.3), metal-salt presence was found to decrease extractant solubility in
H2S04while
increasing it in HCI media. Solubilities decreased From 30 pprn and 20 pprn P, in pure 0.5M
H2SOh to 5 pprn and <0.2 pprn P,in raffinates, with OPAP and D2EHP4 respectively. In
contrast, solubilities increased f?om 10 pprn and 7 pprn P, in pure 6 N HCI, to 13 pprn and
16 pprn P, in HCl strip solutions, respectively. Figure 4.4 shows the effea of metal-presence
on acid medium comparng these same values in units of pprn extractant. Table 4.4: Extractant solubility in I.affinate and strip solutions (A/O=l.O). Extractant (0.95 F) Loading conditions (50C) Stripping conditions (20C)
\ I
Solubility afler 2 houn (ppm P) Conditioned OPAP 1 Conditioned DZEHPA 5 cO.2 13 1 6
Figure 4.4: Effect of metal-salts on aqueous solubility of fiesh extnictants (0.95 F): (a) OPAP; @) DZEHPA Note that OPAP and DZEHPA solubilities become similar during stripping when salt is present with this change in units (168 versus 167 ppm, respectively). High salt content understandably should lower organic solubility by lowering the mean activity of water and
consequently the overall solubility. This appears to be the case under loading conditions.
a s observed. However, under stripping conditions, an increase in organic solubility w

For both OPAP and D2EHPA, more phosphorus (or organic) i s solubilized in the strip feed
than in the aqueous feed. The order of phosphonis solubility in acid+metal salt solutions is
now reversed relative to that in simple acid solutions. Unless a 'salting-in' explanation exists
for the higher levels of organic transfer to the strip solution because of metal-salt presence,
early commencement of metal-catalyzed degradation of the extractants in the strip solution
has to be considered. In the following section, the long-term effects of aqueaus media and temperature on degradation are discussed.
4.1.2 Long-term degradation results
Figure 4.3 shows that OPAP increases in solubility, while D2EHPA solubility remains steady
throughout the two houn of contact under either loading or stripping conditions. This poses
the question as to whether degradation of OPAP is taking place. Comparing OPAP to
DWIPA, the former is expected to be less stable because of its 50% mono-alkyl ester
content, which like hil2EHPA (entirely mono-allcyl ester), may degrade. On the other hand,
D2EHPA appears to also be affecteci by metal-salt presence, at least in the short-term. Long-
terni stability tests were perfomed to determine if these trends were due to degradation. The long-term tests involved vigorous conditions. In operations, the organic phase is not intimately mixed with the aqueous phase on a continuous basis. but rather for intermittent durations of 5-10 minutes. This degradation test involves continuous contacting, therefore not reflecting a tnie plant environment.
4.1.2 1M a t a n t stabilities
Throughout the 32 days of testwork, dl aqueous phases (metal-containing) were clear under al1 conditions following phase separation. The OPAP phase, in contrast to D2EHPq which aiways remained clear (orange-yellow) under al1 conditions, was predominantly opaque (yellow-orange) in the loading tests. At 8 days of total cumulative mixing, OPAP under loading conditions began forming a rnilky white (lemon yellow) emulsion that mexisted
with the normal yellow-orange colour seen. It appeared not to be a third phase, but rather a
portion of the organic phase that had more extensive aqueous entrainment. This milky portion persisted even d e r the time taken for phase separation which had climbed to approximately 14 minutes by this point. Meanwhile, D2EHPA phase separation was always less than 10 minutes throughout the 32-day test. M e r test completion, several days elapsed before the milb OPAP portion completely coalesced. This phenomenon appears to be the same as that encountered with M2EHPA under similar degradation test conditions (Dernopoulos et al 1996). Ac~rding to Figures 4.5 and 4.6, OPAP degradation increased wntinuously with time, but less dramatically at 20C. DZEHPA losses tended to plateau at less than 50 ppm in dfinates
and less than 100 ppm in stnp solutions at both tempenitures. Degradation of not only
OPAP, but possibly D2EHPA as well, appears to occur fiom the start of loading and
stripping when considering Section 4.1.1.2 findings.
1 6
a)
24
28
3 2
T=(days)
(b)
Figure 4.5 : Long-term degradation of OPAP and D2EHPA (0.95 F) i n aqueous feed solution (A/O=l.O; AF= 25 g/L~ e ~ 90 ' , g/L 2n2+,50 glL H2SO4): (a) 20C; @) 50C.
1 2 1 6 2 0 2 8 3 2
8 1 2 1 6 2 0
24
28
3 2
T=(daysl
=mm)
(b)
( 4
Figure 4.6: Long-term degradation of OPAP and D2EHPA (0.95 F) in srip feed solution (NO= 1.O; SF40 g/L ~ d + 6N , HCI): (a) 20C;(b) 50C.
Table 4.5 lists the final residual phosphorus concentrations (after 32 days) dong with the correspondhg values for M2EHPA in similar tests conducted by Molnar et. al (1989). The order M2EHPA > OPAP > DZEHPA is followed in tenu of degradation while in contact with aqueous feed at either temperature.
M2EHPA loading degradation values are
significantly greater than the 90-hour continuous pilot plant finding of 12 ppm P in the
the former representing 1.6 gR. (-0.8%) and 3.1 g/L (-1.5%) losses at 25C and raff~nate,
50C, respdvely. This demmstiztes the sggessiveness of the ?est conditions employed
here. The order OPAP > D2EHPA is followed in t e m of degradation while in contact with the strip solution at either temperature. Corresponding values for degradation in stripping media were not generated for M2EHPA by Molnar et. al (1989), but their magnitude is expected to again be significantly higher than OPAP or D2EWA.
OPAP degraded more readily than DZEHPA under all conditions, but not nearly to the sarne
extent as M2EHPA
Both OPAP and D2EHPA degraded more in the strip solution.
WEHPA had behaved as such &er 90 hours of continuous pilot operation @ernopoulos et
al. 1996), which yielded losses of 12 ppm and 80 ppm P in dfinate and strip solutions, respectively. Table 4.5 : Extractant solubilitydegradation in aqueous and strip feeds (NO-l .O). Solubility-degradation after 32 days (ppm P) 50C 2O0C Extradant (0.95 F) M2EHPA OPAP DZEHPA M2EHPA OPAP DZEHPA 240* 78 15 456* 188 44 Aqueous Feed 552 Strip Feed 133 80 86 *- Mohar et al. (1989) 3 1-day samples at 25C and 50C
4.1.22
Effecto f tempetatun on degr&on
Temperature significantly increased OPAP degradation, especially in the strip solution, with
140% and 300% increases of residual phosphorus content in raffinate and sip solutions,
respectively.
Like OPAP, D2EHPA exhibited best stability in aqueous feed at 20C.
Howwer, in contrast, D2EHPA was not affected as drastically in strip solutions at the higher temperature, as iilustrated in Table 4.5. Based on these findingq ambient temperature loading and stripping is recommended for OPAP.
4.1.23 I r o n m catalysk o f estet hy&olysis
Based on the long-tem degradation results above, it is clear that 1 strong Fq(S04)3-ZnSO&I2SO4
phosphonc acids
degrade significantly more at 20C and 50C in a strong FeCb-HCl strip solution than in a
rafinat e solution, i.e. an apparent generic problem exists. Therefore, certain distinguishing constituents in the stripping medium of interest must be promoting a greater degree of degradation with either M2EHPA, OPAP, or D2EHPA.
Consequently, zhe consideraiion of various mineral acids is required.
It is reasonable to
argue that contact with a pure acid solution should only solubilize the extractant. Following
Lechatelier' s principle, acid in excess of stoichiometric quantities should stabilize, not degrade, the extractanf since acid is a produd of ester hydrolysis. ester + water
acid + alcohol
(4.1)
M2EHPA degradation in the presence of HN03 has been observed by Van Weert et al.
(1998). However, H N a is an exception as the anion NOS-is a potential oxidant while the
other possible mineral acid anions, Cr and S O ,:
are relatively inert electrochemically.
Note, however, that Cr has activity enhancement capabilities. Section 4.1.1.2 showed that extractant solubility, which was lower in pure HCl than in pure H2S04solutions, was higher in strp solution versus raffinate medium in the presence of metal-salts. Comparing the distribution of i r o n o in the aqueous phases under loading and stripping conditions leads to
the observation that there is more fiee i r o n o content in the strip solutions than in the
*nates.
This is because uon(IXI) is being built-up in the former, while being depleted due
to extraction in the latter. Predominant lock-up of aqueous iron(III) as irono-sulphato complexes, according to the speciation diagram given in Figure 2.4, suggests even less available unloaded fiee i r o n o under extraction conditions. With this in mind and additional mechanistic information by Henderson (1993), uon(m) arguably becornes the suspected constituent that promotes degradation. It is therefore postulated that high [fiee
~ e ~ + ]catalyzes , the hydrolysis of organophosphoric extractants to inorganic orthophosphate.
Since the rate and extent of degradation is catalysis-based, higher temperatures would understandably increase residual phosphorus concentrations to higher levels as was illustnited in Figures 4.5 and 4.6. In terms of reaction energeticq high temperature renders activation energy barriers more attainable. According to Henderson (1993), the degradation mechanism involves catalysis by specific
hard acids, of which o n o is included. Figure 4.7 shows the explicit mechanism implied by Henderson (1993). In this example, a mono-atkyl ester is shown to hydrolyze to orthophosphoric acid and alcohol. T h i s also represents the partial hydrolysis of a starting di-alkyl ester molecule producing mono-akyl ester, H m 0 4 which could then hydrolyze again according to Figure 4.7 attaining cornplete hydrolysis. This means that D2EHPA forms
M2EHPA upon degradation, the latter of which more readily undergoes subsequent degradation.
Figure 4.7: Poshilated mechanism for i r o n o catalyzed hydroly sis of organophosphotic acids (based on Henderson 1993).
The mechanism is a dissociation reaaion involving as a first step, the expulsion of an alkoxyl group @O) via the cleavage of a P-Obond. The second step involves water acting as a
Lewis base atiaching itself to the phosphorus centre restoring the desired coordination to the
extractant molecule. The water loses its hydrogen to the alkoxyl group, liberated in the prior dissociation, completing the hydrolytic reaction. Reaction catalysis by iron(m) cornes about by an electron lone-pair of the leaving alkoxyl group oxygen atom forming a coordinate bond
with i r o n o . The electron-withdrawing character of the coordinated iron(m) facilitates the

rate-determining cleavage of the P-Oby withdrawing electron density from that same bond, thereby weakening it.
Some degradation via this rnechanisrn does also occur in raffi~nates since some unloaded tiee
i r o n o does exist, although at lower concentration than in stnp feed. Under loading conditions, a significantly greater portion of the extractant is complexed with iron(1II) than is
the case during stripping. The iron@I)-organo complex i s expected to be more resistant to
degradation due to the electron-withdrawing behaviour of the electron-deficient i r o n o
which is complexed to the extractant. Figure 4.8 illustrates loaded i r o n o via the inductive
effect acting against the cleavage of the P-Omolecule that is encouraged by another iron(III)
h i s counterbalances catalysis, thereby stabilizing the iron(III)-loaded acting as a catalyst. T

extractant rnolecule. In contra& free iron(m) presence as a major constituent in HCI strip solution media is frther enhanced because of an increased i r o n o activity. T h i s increase is
brought about as a result of the lowering of the water mean activity which is caused by the
high HCI and chloride salt concentrations in the strip solution (Jansz 1983).
Fe*
F i g w 4.8: Stabilizing inductive effect on extradant molecule by loaded i r o n o .
The order M2EHPA > OPAP > DZEHPA describes both solubility and degradation. This order also reflects the mono-alkyl ester content in each extractant. As discussed earlier,
mono-alky 1 esters are more aqueous-soluble due to their relative1y lower hydrophobie character. In terms of degradation, mono-alkyl esters (M2EHPA and mono-OPAP)require ody one hydrolytic step to attah complete hydrolysis rather than two as required by the diakyl esters (&OP AP and MEHPA). In addition, the second alkoxyl group in D2EHPA or di-alkyi OPAP gives added electron-withdrawing character which results in an increase in the chernical resistance of the extractant molecule against iron(m) cataly sis by exhibiting the
same inductive effect as shown with loaded i r o n o .
In terms of extractant stability, this catalytic tendency of i r o n o may make direct reductive
stripping treatment of HCl strip solutions more attractive. Conversion of i r o n o to i r o n o limits the exposure of the uncomplexed extradant to free iron(m), thus reducing the extent of extraaant degradation. Although i r o n o is also considered a hard acid capable of catalyzing phosphate ester hydrolysis (Henderson 1993), it should be less effective than iron(m) since iron(II) is less electron-deficient. The same can be said for zinc which may be used in combination with or in place of i r o n o .

4.2
OPAP AND DLEHPA EXTRACTION
Organophosphoric acids readily extract iron(III). As iron build-up is vital to the overall solvent extradion route, the extent to which i r o n o is removed and loaded ont0 the organic phase is important. However, equally important is that this extraction must be highly
selective for iron@I) in order to achieve a pure downstream iron oxide product.
In this section, conditions for 0.95 F OPAP and 1.25 F DZEHPA are identified that yield
optimal loading performance and selectivity. In the previous section, findings indicated that ambient temperature extraction would be the favoured route for OPAP in order to minimize extractant solubilization and degradation. In light of this, the manner in which ambient temperature operation influences loading performance and selectivity characteristics was closely followed in order to assess its technical application. Extraction kinetics tests were conducted to determine the most favourable operating conditions (e.g. temperature and contact time) with respect to efficiency and ~ d ' l ~ nand ~'
Extraction isotherms were also generated to determine the maximum F ~ ~ + / s selectivities. o~-
i r o n o loading capacity, the anticipated raffinate i r o n o composition, the number of

stages required, and resulting pH functionality. No scrubbing procedures were tested.
However, the procedure for organic analysis of loaded zinc and sulphate, that was developed and applied to the experimental organic samples, was used to gather insights into needed scrubbing measures.
4.2.1 Extraction kinetiu and etrciency
Extraction kinetics tests were p e r f o d with freshly prepared OPAP and D2EHPA which were conditioned according to the established sulphuric acid washing method, as given in Section 4.1.1. The effects of temperature, aqueous feed acidity, and t h e were studied. The minimum contact time required to attain practical equilibrium for each set of conditions was determineci. As well, extractant selectivity for iron(IIi) against both zinc and sulphate was monitored in terms of kinetics.
With regard to phase disengagement, both OPAP and D2EHPA tests achieved secondary breaks w i t h i n 80 seconds upon test completion. However, due to the operation being
aqueous continuous, all raffinates were centrihged to remove residual entrained organic.
The OPAP and D2EHPA organic phases exhibited their usual appearances of a semi-opaque yellow-orange and a clear orsinge-yellow colour with 50 g& initial &SO4 aqueous feed. However, minor coalescence problems were encountered by both extractants with the low acid (12.5 g/L &SO4) aqueous feed. OPAP was more cloudy than at higher acidity with some waxy solids present at the organidaqueous interface, and the D2EKPA phase included large droplets (2-5 mm diameter) that required additional time to fblly coalesce. However, this behaviour is of no practical concern as low acidity is not relevant to the anticipated HAL feed solution which contains 50 g/L H2S04.
4.2.1.1 Effect o f acid concentration und tempetatute on iron(m) attaction efficiency
Figure 4.9 plots extraction efficiency against time for each of the kinetics tests. Comparing the extractants, OPAP exhibited more favourable iron(m) extraction kinetics and efficiency
than DZEHPA.
In terms of acid effect, OPAP required 10 minutes to attain practical equilibrium with a
50 g/L&SO4 aqueous feed at either temperature. D2EHPA also required 10 minutes with 50 g/L H2S04aqueous feed at 50C. As expected, lower aqueous feed initial acidity (12 g/L
&SO4) improved the efficiencies of each extractant at either temperature.
T h i s improvement
was marginal in the case of OPAP (0.5-2%), which reflects its good pH fbnctionality, but more substantial ( 6 4 % ) for DZEHPA In terms of temperature, OPAP exhibited better efficiency, on the order of 100/o (at 20C) and
5% (at 50C) higher than D2EHPA with 50 g/L H2S04 aqueous feed. Operation at ambient
temperature with 50 g/L
aqueous feed would involve a reduction in the efficiency of
OPAP of 5.5% at 10 minutes and for D2EHPA a 9.W decrease at 30 minutes of mixing.
h i s The D2EHPA efficiency losses would increase to 18% with shorter mixing times. T means that D2EHPA would require greater than 30 minutes of contact time compared with
OPAP for the same extraction. Hence, the use of DZEHPA at 20C during extraction appears
highly undesirable fiom the perspective of either efficiency or kinetics.
IcesctionTm (min)
@)
Figure 4.9: Iron(m) extraction kinetics for: (a) 0.95 F OPAP;@) 1.25 F D2EHPA, (A/O=2.0; no acid control).
4.23.2 Zinc cu-dracrion as afuncii*ono f time
As already known with M2EHi?A (Demopoulos et d 1989, 1996), zinc has faster loading
kinetics than iron(III). Zinc concentration in the organic phase decreases as a function of
time as a result of unloaded iron(LII) displacing initially loaded zinc. Table 4.6 shows that
the levels of zinc CO-extracted ont0 OPAP and D 2 m A in the same kinetics tests decreased with time. Having now seen this behaviour with OPAP and D2EHPq in addition to what is known about M2EHPq it is evident a . this point that this phenornenon is a characteristic of
al1 organophosphoric acid extnictants.

OPAP initially loaded more zinc, but quilibrated to a comparable, although slightly higher,
level than that seen with D2EHPA. A contact time of 10 minutes was required to attain the
minimum zinc concentration in both extractants.
Table 4.6: Zinc loading (NCF2.0;[H2S04]p50g/L).
Contact Time (minutes)
[ 2 n 2 ' ] in organic phase @pm) 0.95 F OPAP ( 2 0 0 ~ ) l 1.2s F DZEHPA (50C)
4.2.1.3 Su$hute co-exthzction as afunction o f tinte
Table 4.7 shows the amounts of sulphate cwxracted by OPAP and D2EHPA in the kinetics tests. DZEHPA loads greater than 20 times the amount of sulphate loaded by OPAP. Contraxy to zinc behaviour, sulphate CO-extractionincreased as a function of time for both extractants, with no apparent upper limit detected for contact times less than 30 minutes. Table 4.7: Sulphate loading (AI(P2.0; [H2S04l0=50g L ) .
.. . .
Contact Time (minutes)

2
[SO:~ in organic phase @pm)
0.95 F OPAP (20C) 20
1.25 F D2EHPA (50C)

1480
4.2.2 ~e*/Zn'+ and I?e*/S0:-
extraction selectivity
Having initially looked at zinc and sulphate co-extnidion in terms of kinetics, focus will now
shifi to understanding selectivity at equilibrium. Acid and temperature effects were again considered.

1X21 E n d o f acid coneenbdon on ~d+nn'+ selectivity
Figure 4.10 shows that at bath temperatures OPAP ~ e ~ + / zselectivity n~+ (SgFJZnl=DFJDZn) improved as acidity increased up to 25 g/L, with no further improvement at higher acidity
levels.
Figure 4.10: OPAP (0.95 F) ~ e ~ + /selectivity ~ d + as a fnction of initial acidity (A/=2.0).

Figure 4.1 1 compares OPAP and DZEHPA ~ e ~ + l ~ selectivities n'+ against initial acidity. Here, it is shown that DWIPA selectivity also increased with increasing acidity. It is known
that for the organophosphoric acid extractants, the zinc pH-extraction curve is located in a
higher pH region than that for iron@I) (Ritcey et al. 1975). The extraction curves show
individual metal distributions as a finction of equilibrium pH for a particular extractant.
Zinc extraction decreases to zero et a certain equilibrium pH. I r o n o extraction begins to

decrease substantially only at a lower relative equilibrium pH, which would represent initial n~+ factor increased nom acid levels above 75 fi H2S04. Therefore, the ~ e ~ + l Zselectivity
12.5 g/L to 50 g/L initial H2S04 for either extractant, since at these acid levels, the
distribution of h n o remained unaltered while that of zinc apparently decreased substantially.
n'+ as a Figure 4.11: 0PAP(0.95 F)-DZEHPA(l.25 F) cornparison of ~ e ~ + / ~ selectivity function of initial acidity (A/O=2.0): (a) 20C; @) 50C.
4.2 2 2 Effecto f temperature on ~ d + n n ~ selectivity +
Figure 4.11a shows ~ e ~ + l ~ selectivity n'+ for OPAP at 20C being higher than that of
D2EHPA at 20C.
Considering the 50 g L HzSO4 aqueous feed, the corresponding
selectivity factors were 3000 and 1063, respectively.
This partinilar aqueous feed
composition will be used as a reference point as it reflects the anticipated HAL solution composition. Figure 4.11b shows a dramatic reversal in the order of OPAP and D2EHPA
selectivities. OPAP ~ e ~ ' / ~ nselectivity *+ decreased w i t h the higher temperature of 50C

while that of DZEHPA increased to an extent such that DZEHPA had the greater selectivity.
Considering again the 50 g/L H2S04 aqueuus feed, the corresponding selectivity factors were
850 and 3700 for OPAP and D2EXPA at 50C, respectively. OPAP exhibited its greatesi
iron(m) selectivity over zinc at the lower temperature. Otherwise OPAP at 50C was less
selective than D2EHPA at 20C or 50C, using the 50 g/'LHzS04 aqueous feed. Therefore,
operation of OPAP loading at 20C and D2EHPA at SOC is recommended. Arnbient extraction conditions for OPAP appear acceptable as the extractant yielded comparable i r o n o loading efficiency (33%, Figure 4.9) and zinc co-actradion (Table 4.6) with
D2EHPA at 50C, if the contact time in both cases was 10 minutes. In t e m of ~ e ~ + / Z d +
selectivity at the recommended conditions for each reagent, D2EHPA at 50C is marginally
better than OPAP at 20C (3700 versus 3000 with 50 g/LH2S04aqueous feed).
4.2.2 3 Effecto f ocid concenttation and tempetuture on
seleca'vity
In Section 4.2.1.3, it was reported that sulphate c~extraction increased with contact time.
Sulphate cm-extraction was also found to increase wih increasing acidity for both extractants at either temperature. Figures 4.12 and 4.13 show OPAP and DZEHPA F~~+/SO?' selectivity factors (Sv~)=DFJDsac)decreasing with increasing acidity. Increasing sulphate
CO-
extraction with increasing acidity is expected as higher &SOI presents a higher concentration of sulphate, which forces more of the latter to distribute onto the organic phase.
This trend was followed by both extractants with aqueous feeds containing up to 50 g/L H2S04 or more. A selectivity (SrtFdS041) value of 1305 was determined for OPAP at 20C
with the 50 glL H2S04 aqueuus feed, conditions which sirnulate the application of OPAP iction at optimum conditions.
2500
IOPAP(20C)
0OPAP(5O0C)
2000
Q
w
0 1500
1000
500
O
13.5
25
50 [ H ~ S O(Bn) ~O
75
Figure 4.12:OPAP (0.95 F) F~+/so> selectivity as a function of initial acidity (A/O=2.0). Previously, it was shown that sulphate loading was significantly less onto OPAP than onto
D2EWA Figure 4.13 compares selectivity factors of the two extractants showing that the
selectivity of OPAP i s greater by a factor of -10 at dl acidhemperature conditions. Figure 4 . 1 3 b shows how low D2EHPA selectivity can be (in the range 40 to 55) as compared to
OPAP selectivities of around 600 at the higher temperature and over 1000 at the prefexed
lower temperature of contact (Figure 4.13a).
The F~~+/SO;-selectivity of both extraaants decreased with increasing temperature. For

D2EHPA, increasing the temperature fiom 20C to 50C had a relatively minor effea,
decreasing an already low S W ~ mresult ) of 150 down to 40 with 50 g/LH2S04 aqueous

feed. However, the effect was more dramatic for OPAP where Sve/so4> decreased fiorn 1305
to 575, M e r supporting the use of ambient loading conditions. Based on this, it can be concludeci that OPAP at 20C offers by far the best selectivity for i r o n o over zinc and sulphate.
Figure 4.13 : 0PAP(0.95 F)-DZEHPA(1.25 F) cornparison of F ~ ~ ' / S Oselectivity ~~as a function of initial acidity (AKb2.0): (a) 20C; (b) 50C.
4.2.24 Eleconic and s t i c Mec& conducive & high F ~ + / s o ~ selectivity *
Electronic and stenc effects on the kinetics of ligand substitution may explain the lower sulphate cwxtraction exhibited by OPAP relative to DZEHPA The greater electronwithdrawing capacity of octylphenyl groups of iron@I)-coordinated di-OPAP exhibit a
greater 'neighbou~gligand effect' than the 2-ethylhexyl groups of iron(III)aordinated
D2EHPA (Wilkins 1991).
If metabligand associations were considered in terms of
molecular orbital bonding, rather than atornic orbital or coordinate bonding, then by withdrawing electron-density fiom an iron@I)-sulphate bond, the octylphenyl alkoxyl groups
@O) will increase the lability of the coordinated ligand sulphate. This is illustrated in Figure
4.14. However, the ligands need to be situated p a n s to one another for this to occur. Hence,
the merits of such an efTect are questionable, as none of the RO groups can ever be situated
a a r t s to sulphate in a pure sense.
Figure 4.14: Conceptual i r o n o oaahedron in a non-equilibrium loaded organic phase containing di-alkyl organophosphonc acid extradant. Dunng extraction, it is unlikely that bullcy organophosphorus extractants such as D2EHPA or di-OPAP exhibit any associative ligand exchange. This is simply because of the unfavourable steric strain that would result from the increase in coordination number to -7, which is required by the pseudo-transition state of that mechanism. Instead, more favourable relieving of stenc congestion is likely to occur where iron(TII) coordination decreases from 6 to -5, as required by the pseudo-transition state of a dissociative mechanism. Conceivably, increased bulkiness should increase the dissociative reaction rate. This favoun the larger diOPAP moleeule. Its larger alkoxyl groups should m a t e a greater steric crowding effect that discourages sulphate loading and 'pushes out' aiready coordinated sulphate as uon(m)
h i s would result in a lower sulphate CO-extractionthan loading approaches equilibrium. T

with DZEHPA In temis of thermodynamics, a stability constant analysis, highlighted in Appendix B, predicts that iron(m) coordinates more strongly with organophosphates than inorganic sulphate. It is likely that the inherentiy slow ligand exchange kinetics of i r o n o
with wordinated sulphate will be made faster by the steric hindrance brought about by di-
OPAP, favouring more exclusive irono-OPAP coordination.

4.23 I r o n o loading characteristics
In Sections 4.2.1 and 4.2.2, ambient temperature extraction with OPAP was reported to
and produce acceptable iron(m) loading eficiency and selectivity (in terms of D F J D ~
DFJD-)
results, comparable or preferable to those yielded by OPAP at 50C or by
D2EHPA at either temperature. To measure the expected negative impact that ambient
temperature operation will have on loading, McCabe-Thiele analysis was conductecl on the i r o n o extraction isotherms. From this work relevant engineering parameten were estimateci including phase separation characteristics, maximum i r o n o loading capacity, raainate i r o n o composition, and the number of required loading stages for a continuous counter-curent circuit.
4.2.3.1 Phase sqwation characteristics under mhzction conditions
Concerning phase separation times, d l OPAP test contacts under aqueous continuous conditions gave very consistent r a b . Primary and secondary break times were 30 seconds and <5 minutes, respectively. DZEHPA separated very quickly from al1 *nates,
requiring
less than 60 seconds to achieve a very clear aqueous phase. Organic continuous operation required longer separation times. Specificdly, with 50 g/L H2SO4 aqueous feed at O/A=1.0,
OPAP required 4 minutes separation time at 20C and 7 minutes at 50C. DZEHPA again
separated very quickly, requiring <2 minutes. As found with MZEHPA (Dernopoulos et al.
OPAP and D2EHPA chernical performances were assumed to be the same regardless of phase continuity.
1996),
In ternis of phase clarity, finates
were wnsistently cloudy under aqueous continuous
conditions and consistently clear under organic continuous conditions when using OPAP. In
the former case, a number of raffinates were centrifugeci to remove the persistent cloudiness.
-nate
clarity was found to increase with increasing acidity. D2EHPA yielded two clear
phases at al1 O/A ratios in its one set of conditions. Typically, the clarity of both OPAP and D2EHPA organic phases resembled the kinetics test findings described in Section 4.2.1.
OPAP solution opacity and orange colour were observed to inaease with the extent of
loading.
There was some evidence of possible cmd formation. A rninor amount of waxy residue,
d l y located at the organidaqueous interface, tended to form under aqueous continuous operation, usually at O1A phase ratios 0.25 and 0.50 for OPAP. This appearance was dependent on neither temperature nor initial aqueous phase acidity. Some interfacial residue
was also observed with DlZEHPA at O/A=2.0.
Notable coalescence problems resulted that were characterized as dispersion 'bubbles' in the organic phase. These 'bubbles' delayed complete phase separation until 10 minutes d e r the end of mixng. For OPAP, this behaviour was not dependent on temperature, tending to appear at O/A phase ratios 0.50 and 0.75. Very similar characteristics were exhibited by
D2EHPA for the same contacts, even to some extent at O/A= 1.O.
In the case of OPAP, a secondary coalescence problem was evident which consisted of
aqueous entrainment in the organic phase where there existed 'two phases' (dark orange and
lemon-yellow), as was observed in the degradation tests discussed in Section 4.1.2. Otherwise, the quality of the interface and raffinate indicated complete separation. This
behaviour which followed no apparent trend with OPAP, was not encountered with
D2EHPk
4.2.3.2 M w * m m workable &actant
concentrations
Extractant concentrations of 0.95 F OPAP and 1.25 F DZEHPA were adopted for al1
expenments other than the solubility-stability work, and certain stripping tests which employed 0.95 F D2EHPA. Al1 preparations included 20% d o (0.84 F) tridecanol for the reason that this reagent proved an effective modifier in previous M2EHPA work during loading @emopoulos et al. 1996). The extractant concentrations chosen were the maximum workable arnounts. To support this Its concentration was selected based on the low associated zinc CO-extractionthat occurred
daim, stable emulsions were encountered with W.95 F OPAP organic solutions in
preliminary test w o r k As wei, upon prolonged stomge, a precipitate was found to result with loaded 1.25 F (40% d o ) D2EHPA solutions. T h i s latter finding was surprishg since
D2EHPA has been reportedly used at concentrations of 50% v/o (Tabor 1999) and 60% v/o
(Sahu and Das 1997). However, in these cases, no modifier was used and the organic phase
cunsisted simply of D2EHPA and kerosene. The D2EHPA concentration chosen here was based on work by Ritcey and Ashbrook (1984).
Steric effects on thermodynamic stability explain why i r o n o loaded OPAP may be more
stable than iron(III) loaded DLEHPA.
Bulky organophosphoms ligands on i r o n o
introduce increased molecular ordering, which lowers the entropy of the system. In t m s of energeticq this unfavorable effect of bulkiness manages to be counter-balanced by resulting increased hydrophobic interactions which can stabilize iroro-organo complex aggregation. OPAP is bulkier than D2EHPA and hence, has a greater hydrophobic stabilizing effect as crowding occurs. In addition, the 'chelate effect' does more than offset the entropy drop. Attached organophosphoms ligands increase the overall number of independent species, upon extraction, by liberating the more numerous single non-chelating species, thereby increasing disorder.
4.2 3.3 Iron ( n l ) extradon isotherm~
The extraction isotherms for iron(IiI) are given in Figure 4.15. They indicate that the loading capacity of D2EHPA is lower than that of OPAP at the conditions tested. The 1.25 F D2EHPA isothenn predicts a loading capacity of 16.5 gR. iron(III) at 50C with 50 g/L H2S04aqueous feed. T h i s is a conservative estimate as loadings in actual test work yielded
19.5-20.5 g/L iron(III). For OPAP, decreasing temperature lowers loading capacity by 12%
and 17% for 15 g/Land 50 g/L H2SO4 aqueous feedq respectively. With 50 g/L H2S04 aqueous feed, predicted capacities decrme fiom 21.0 g/L iron@[) at 50C to 17.5 @L i r o n o at 20C. This means that opting for ambient temperature extraction with HAL solution feed incurs a loss of -3.5 g/L loaded iron(m). Amal OPAP loading values by two successive contacts at 50C with 50 g/LH2SQ aqueous feed were 20.5-21.5 g/L i r o n o , which confimi the conesponding isotherm prediction. Inaeasing aqueous feed acidity has less effect than decreasing temperature on the predicted
OPAP loading capacity. The marginal decrease in loading uipacity because of increased
aqueous feed acidity reflects the good pH functionality of OPAP. OPAP pH functionality is evident at both temperatures in Figure 4.16 which plots the OPAP isotherms paired in terms
of cornmon operating t e m p e m e . McCabe-Thiele analysis was performed on the 20C and
50C isotherms using 50 glL H2S04 aqueous feed. With an A I M . 7 0 operating line, the
20C and 50C isotherms predict a raffinate containing less than 0.5 g/L iron(III). However,
such a low residual i r o n o concentration in the dllnate is not necessary as some iron(III) content is required in the recycle Stream to the neutral Ieach for impurity scavenging
purposes. Opting for OPAP operation at 20C requires a third stage, one more than expected
at 50C in a counter-curent extraction circuit.
Figure 4.15: I r o n o extraction isothems for OPAP and D2-A
(no acid control).
20
5
Ct
e;
$ f
m
k 5
10
f7 x0
Figure 4.16: I r o n o extraction isothems for 0.95 F OPAP: (a) 20C; @) 50C;(LO =loaded organic; AF = aqueous feed; SO = stripped organic; no acid control).
4.2.4 2n2+ and ~011-scrubbing
Organic sample malysis condinons
The scrubbing procedure developed for the removal of co-extracted zinc and sulphate f i o m loaded organic samples was penormed at 20C and an O1A phase ratio of 0.50. The organic phase was prepared by diluting the sample aliquot with a kerosene-tridecanol solution. In order to develop the procedure, the organic solution was pre-loaded in two separate series of
tests, either with
zinc by contacting it with pH 4 ZnS04 solution, or with suiphate by
contacting it with 75 g/L,H2S04 Ratfinate samples were taken for analysis to determine indirectly the amount of zinc or sulphate that was loaded onto the organics. Each loaded organic solution was then scrubbed with consecutive contacts of fiesh dilute HCi in an attempt to effectively remove zinc and sulphate. Various dilute HCl scrub feed compositions were screened. M e r mixing, the phases were centrifged and the scnib liquon were
sampled for analysis. A secondary scnib liquor generated fiom a subsequent single 6 N HCI
'check' contact was sampled and analyzed tu confkm thai scrubbing was complete.
ReliltllbnatyinfoRtlQriZboon for scrubbing masures
The results of these screening/development tests not only provided an analytical preparation
technique, which is detailed in Section 3.3.3, but also provided preliminary raw data on scrubbing stage engineering and operating conditions. The saub feed seleded was 30 g/L
(0.82 M) HCI, which was found to adequately remove both zinc and sulphate, but also
removed some uon(m) under conditions where iron(m) pre-loading was also involved. Although i r o n o removal is undesirable in a scmbbing circuit, it was an non-issue in terms
of sample stripping analysis. Table 4.8 shows that only two contacts were required to scmb
al1 of the loaded zinc fkom organic samples. Table 4.9 shows that it was more dificult to remove the loaded sulphate, as five contacts were required. The s m b liquors fiom the 6 N HCl 'check' contacts contained negligible quantities of zinc or sulphate, thereby confirming that two and five contacts completely scnibbed dl the zinc and sulphate, respectively. Further work is necessary to investigate the effect of high chlonde salt backgrounds, MgClfiech, to accompany HCI concentrations iower than 30 g/L (0.82 M). Less acid would avoid premature i r o n o stripping and a high salt concentration would present chloride in such excess quantities hat sulphate scrubbing eficiency would increase, since scnibbing is believed to be an exchange of anions Cl' and SO?-, as given in Equation 2.7. Table 4.8: Evaluation of zinc-loaded OPAP sample m b b i n g (20C; O/A=.SO). Contact
1 2 3 4 5
1.45 g znZ'/L OPAP 1.87 gzn2'/L OPAP 2.07 gzn2+/LOPAP mg Zn2' % rngznz+ % mgzn2+ % scrubbed strippd Scnibbed stripped smbbed stripped 1.44 99.3 1.85 98.9 1.97 95.2 0.0 1 100.0 100.0 0.03 100.5 O. 10 0.00 101.1 100.0 0.0 1 101.1 100.0 o*oo 0.00 100.0 0.00
Table 4.9: Evaluation of sulphate-loaded OPAP sample scrubbing (20C; OIA=0.50).

Contact
3.52 g SO~YL OPAP mg so? %
6.95 g SOCIL OPAP mg ~ 0 4 ~ - % scrubbed stripped 69.4 4.82 0.29 73.5 1.O7 88.9 0.53 96.5 0.24 1 100.0 1
scrubbed 320 O, 14
0.03 O. 15
stripped 90.9
94.7 95.6 99.9
1 0.00 1
100.0

4.3
OPAP AND D2EKPA STRIPPING
Effective iron(m) extractants typically form strong complexes which render subsequent
stripping difficult. This poor stripping behaviour is characterized by high i r o n o retention and a large number of required contacts in counteriwrent stripping circuits. This ultimately l a d s to an inadequate concentration of i r o n o in strip solutions. Approaching stripping conceptually in combination with pyrohydrolysis necessitates the use of a strong HCl
solution as the stripping agent for OP# and D2EXPA. As alluded to prc~ioudy,neh5er of
the two candidate extnictants have, if at dl, been credibly investigated with HCl stripping.
T h i s is mainly because research has historically emphasized iron(III) extraction investigation

over that of stripping. The challenge is to quanti@ the extent and manner in which both OPAP and DZEHPA can be stripped with strong HCl and, in an attempt to enhance this performance, an electro-reductive stripping technique was also investigated. Specifically, fiom kinetics test results, the effects of contact time and initial HCl concentration on eficiency were studied. Stripping isotherms were examined, via McCabe-Thiele analysis, to determine the maximum anainable iron
Y)
build-up in the stnp solution, the predicted arnount of i r o n o retention in the organic, and
the number of stages required in a counter-current stripping circuit. Also, the effea of
i r o n w presence, as FeClz, on stripping performance was studied extensively. Like zinc and sulphate during extraction, chloride retention, via some form(s) of backextraction ont0 the organic during stripping, presents serious interphase cross-contamination problems. Although no m b b i n g procedures were developed or tested here, a bench-sale M2EHPA (chloride) m b b i n g procedure developed by Dernopoulos et a L (1996) was applied. Analysis results of backemcted chloride fiom stripped organic samples were used to gather insights into the stripping mechanisms involved with OPAP and D2EHPq in an attempt to explain some of the associateci stripping difficulties.
This section concludes with test results that confnn the expected poor performance of HN@
as a strippant for OPAP, as has been reported for DZEHPA (Van Weert et a l . 1998).

43.1 Stripping kinetics and effciency
With regard to phase disengagement, both OPAP and D2EHPA kinetics test senes achieved primary and secondary breaks in 30 seconds and 2-3 minutes, respectively. Al1 strip solution samples were centrifbged due to some persistent cloudinesq Le. entrained organic, that was characteristic of aqumus wntinuous operation. T h e stripped OPAP and D2EHPA organk
phases had their usual slightly cloudy yellow colours, typical of these organics d e r
conditionhg and pnor to loading.
4.3.1. I Sbipping kineks
OPAP and D2EHPA exhibit similar stripping kinetics. Figure 4.17 shows the percentage of
ironw) stripped versus time. OPAP required 2 to 5 minutes to main practical equilibrium.
DZEHPA regched equilibrium at or below 5 minutes, which is surprising considering the

slow kinetics (>30 minutes) reporteci by Delmas et d.(1996)with 2 M H2SQ as strippant.
In Figure 4.17b, data points for 20 minutes and 30 minutes contact times for D2EHPA have
not been ploaed as the results were the same as at 10 and 15 minutes. Both extractants appear to strip as quickly in single contacts as did M2EWA which required only 2 minutes,
as shown in Table 2.3.
Figure 4.17: I r o n o stripping kinetics for: (a) 0.95 F OPAP; (b) 0.95 F D2EHPA; (20C, O/A=O.SO; ~ d 7 , ~ = 1 8 . 3g/L (OPAP)and 13.8 giL (D2EHPA); no acid control).

4.3.1.2 Effeet o f d d concenbotion on stripping eflcieency
Figure 4.17a shows that OPAP stripping eficiency at mom temperature increased with increasing strippant concentration, Le. 4 N HCI < 6 N HCI < 8 N HCI. The efficiencies yielded &er 5 minutes were 28%, 54%, and 82% for 4 N, 6 N, and 8 N HCl respectively. Although appearing attractive at this phase ratio, none of the subsequent isotherms generated
i t h 8 N HCI strength. Because of HCI azeotrope limitations, pyrohydrolysis were tested w

cannot regenerate acid for make-up of a recycled strip feed containing 8 N HCl if a closed acid loop conceptual flowsheet is envisioned. The pertinent conceptual flowsheet material balancing issues are discussed in Appendix C. Figure 4.17b shows that for DZEHPq stripping followed the opposite order (4 N HCl > 6 N HCl > 8 N HCI) with enlciencies of 89%, 82%, and 39% &er 5 minutes for 4 N, 6 N, and
8 N HCI respectively. T h i s behaviour does not appear to agree with that reported by Sahu
and Das (1997) for 1.9 F (60% v/o) D2EHPA which was characterized by an increase in
stripping efficiency as the initial stnppant concentration increased to 200 g/L or 5.5 N H C I .
T h i s is illustrated in Figure 4.18. However, the curve does appear to develop a plateau at
-6 N HCI which does not rule out the possibility that the eficiency may decrease between
6-8
N HCI. If so, the discnpancy in the initial HCI concentration ranges where stripping
efficiency radically decreases is likely due to the higher concentration of DZEHPA solution
used by Sahu and Das: 1.9 F (60% d o ) wmpared to 1.25 F (41% 40). Opting for the use
of 1.9 F DZEHPA as an alternative to 1.25 F D 2 W A appears attractive with its higher
associated loading capacity (28 g/L iron(m)). However, its use in this application was not considered as the pmblematic degradation and sulphate co-extraction tendencies associated
with 1.25 F D2EHPA would surely be augmented with 1.9 F D2EHPk
Figure 4.18: Effect of hydrochloric acid concentration on iron(III) stripping; (2SC; O/A=l .O; 1.9 F (60% do) DZEHPA; ~e~'],=28.0 g/L; no acid control) (data taken from Sahu and Das 1997).
nie iron(III)-chloride speciation diagram reported by Aprahamian and Dernopoulos (1995) at

20C, given in Figure 2.5, predids that the species FeCbo predominates with FeCl;
approaching the concentration of the former as the HCI concentration increases from 4 to 8 N HCl at equilibrium. Only qualitative deductions may be made here since Figure 4.17 b refers to the initial, rather than equilibriurn acid concentration. Even so, it is pomilated that and,or " FeCIi species, due to the high extensive back-extraction of i r o n o as ~ e C 1 ~ concentration of HCl present, is the cause of the anomalous behaviour observed in Figure
4.1%
Figure 2.3, an uon(m) extraction distribution coefficient versus initial acid
concentration diagram for 0.05 F D2EHPA by Sato et al. (1985), reflects the observed reverse order. The i r o n o extraction distribution coefficient (DF,) is shown reaching a
minimum between 4-5 N initial HCI then increasing dramatically with higher initial acid concentrations (up to 10 N HCl). Figure 4.19 compares OPAP and DZEHPA stripping results in ternis of extraction distribution coefficient, with data taken fiom Figures 4.17 and 2.3. OPAP showed the expected decline in Dn (5.13 to 0.43) f?om 4 N to 8 N initial HCI, reflecting the improved stripping efficiency in that aame acid range. However, as shown in Figure 4.19b,D2EHPA showed a rise in DFc(0.24 to 2.93) which qualitatively appears to &or the a w e by Sato et al. (1985). This back-extraction postulation is m e r developed in Section 4.3.6.
initiai HC1 Cmceotratim(N)
Figure 4.19: Iron(III) distribution in OPAP or D2EHPA and hydrochloric acid at 20C: O/A=SO; @?e37,,,=i8.3 g/L (0.95 F OPAP) and 13.8 g/L (0.95 F D2EHPA); 5 minutes contact time; no acid control; (0.05 F D2EHPA data taken from Sato et al. 1985).
4.3.2 Stripping characteristics
In Section 4.3.1, it was shown that stripping OPAP with 6 N HCl yielded higher efficiencies
than with 4 N HCl. For this reason and the fact that the use of 8 N HCf is not feasible in a stripping-pyrohydrolysis coupled flowsheet in terms of acid baiance needs, 6 N HCI was the
selected stnp feed composition for both OPAP and D2EHPA for the testwork reported in this section,
McCabe-Thiele anaiysis was performed on the generated uon(m) stripping isotherms for
both 0.95 F OPAP and 1.25 F D-4 estimated.
4.3.2 I Phase sepmation chmacteristics undet stniping conditions
from which relevant engineering parameters were
Al1 OPAP and DZEHPA test contacts under aqueous continuous conditions consistently gave secondary break times of 5 minutes or less. Organic continuous operation required much longer sepmtion t i m e s for both extractants as was suggested by HCl solubility tests in Section 4.1.1.1. Ten minutes or longer separation time was required for both OPAP and
D2EAPA at O/A=1.0. At OIA phase d o s 4.0-10, where the organic phase was continuous,
phase separation was even slower (10-20 minutes) for both
extfsfctants.
In many cases at
these phase ratios, the entire tank contents were centrifuged to recover the strip solution
because stable emulsions tended to f o m In ternis of phase c l * ,
the strip solutions were
consistently cloudy under aqueous conthuous conditions with either extractant. Due to this,
a number of strip solutions were centrifigeci to remove the persistent cloudiness. All stnp
solutions were clear with either extractant under organic continuous conditions. In either phase continuity, OPAP and DZEHPA organic phases were opaque, entraining small amounts of aqueous phase. No evidence of any crud formation or coalescence problems were obsented.
4.3.22 IronPI) sdipping isothetrns
Figure 4.20 shows the 6 N HCI stripping isotherms at 20C for OPAP and DZEHPA McCabe-Thiele analysis predias that each extractant will require 3 stages in a countercurrent stripping circuit, considerably fewer than the 8 stages required for M2EHPA (Dernopoulos et al. 1996). OPAP and D2EHPA had similar i r o n o build-up in the strip solution of approximately 30 g/L. However, this is inadequate for pyrohydrolysis as 100 g/L or more i r o n w build-up is required. The nature of the isotherm curves suggests that the
OPAP maximum will likely be higher in practice than that of D2EHPA.
(a)
(b)
Figure 4.20: Stripping isotberms using 6 N E l (initial acid) at 20C for: (a) 0.95 F OPAP; (b) 1.25 F DZESIPA; no acid wntrol; (LO = loaded organic; SF = stnp feed; SL=strip solution; SO = stripped organic).

4.3.3 Effect of FeC12 on stripping
In the two previous sections, 6 N HCl was used in both sets of stripping kinetics and isotherm tests. Adequate uon@I) build-up in the strip solution was not achieved by either extractant.
In this section, these kinetics and isotherm tests were repeated, again using 6 N HCl, but this
t i m e in the presence of 30 gR,40 g/L, or 70 g/L iron(II) as FeC12. Supplementary tests were
i t h and without the presence conducted which compareci 6 N HCl (initial acid) performance w
of 70 g/L iron[II) at OlA4.O and 20C. One equilibrium test was perfonned at 50C to
confinn the expectation that the influence of temperature would not be significant. The
overall purpose was to evaluate the effects of iron(ZI) on OPAP and D2EHPA stripping, in order to observe any stripping performance enhancement tendencieq as well as to try to build up a total iron(II,m) stnp solution concentration above 100 fi.
With minor exceptions, phase separation characteristics were found to be identical to those
observed with pure HCl strip feeds under similar conditions. However, there was a slight decrease in the separation time required for DZEHPA fiom 6 N HC1-70 g/L b o n 0 strip solution under organic continuous conditions. Also, FeC12 presence, at least at O/A=0.50,
gave clearer organic phases upon phase separation. Hence, some minor phase separation
improvements were attribut4 to the presence of FeC12.

4.3rnf 1 Effcto f FeC12 on sbipping Rinetics and mciency
Figure 4.21 shows kinetic tesis cornparhg 6 N HCl strip feed results to those that involved
6 N HCl-FeC12 strip feeds. It was found that the presence of Fe&
had little or no effect on
either OPAP or D2EHPA stripping kinetics. At an O/Aphase ratio of 0.50, the presence of FeCll had a positive effect on OPAP stripping efficiency. In Figure 4.21, OPAP stripping eficiencies with 30 g/L and 70 g/L i r o n o
modestly improved the 6 N HCl resuit of 55.5% to 60% and 57.4%, respectively, after 10
minutes contact.
5
s i [ -
10
5
Conkt T
1 0
1s
i (min)
Figure 4.21: Effect of FeC12on i r o n o stripping kinetics for: (a) 0.95 F OPAP; @) 0.95 F DZEHPA; no acid control; (20C, O/A=.50; 18.3 g/L, and 13.8 g/L for OPAP and D2EHP4 respectively).
L It is arguable that the greater relative eRct by 30 g/L,i r o n o may be explained by the 70 g
iron(I1) concentration being near the uon(II) solubility limit in 6 N HCI. According to this argument, solubility limitations are likely to offset the enhanced stripping power resulting
fiom the increased proton activity that was due to the high background of Fe&. Figure 4.22
plots solubility data taken fiom Silcock (1979). Specifically, Figure 4.22a shows the separate effkcts of HCl concentration on km@) and i r o n o solubility. lion@) solubility is shown to decrease fiom 245 g/Lin water t o 64 g/Lin 6 N HCl at 20C. This latter value being below 70 g/L iron@) is explainable by noting that the equilibrium acid level is actually lower
than the initial 6 N HCI, because protons have been taken up by exchange with loaded
i r o n o during non acid-wntrolled stripping. Iron(III) solubility on the other hand is shown to increase with increasing HCl concentration. According to Figure 4.22b, increasing iron@) concentration does deaease iron(IQ concentration in water. In water, 70 g/L iron(Il) will limit iron(III) solubility to -88
fi. Howwer, Figure 4.22a indicates that the presence of 6 N
HCI will likely increase, not decrease, the 88 g/L value further. Therefore, the combination of high HCI and iron(II) concentrations (Le. 6 N HCl-70 g/L i r o n o ) does not necessarily impose iron(IiI) solubility limitations that limit iron buildup in the stnp solution to impracticably low levels.
4. ResuIts and Diswssion
Figure 4.22: Iron(II,m) solubility data at 20C: (a) FeC13-HCl-H20and FeC12-HCI-H20; @) FeC13-FeC12-&O; (data taken f?om Silcock 1979).
In contrast to OPAP stripping, FeCh presence had an opposite effect on DZEHPA stripping
at an O/Aphase ratio 0.50. D2EHPA efficiency with 6 N HCI drops fiom 82% to 26% with
70 g/L iron(II) present, as shown in Figure 4.21b. Another possible expianation for the
modest (OPAP) or strongly negative @2EHPA) effects of the presence of FeCI2 on stripping
performance is that the increased presence of chloride may enhance iron(m)-chloro
h i s may cause iron(m)-chloro complex back-extraction, although the effect complexation. T

would be significantly greater with DZEHPA than OPAF. Figure 4.23 shows how the
iron(IU) stripping distribution coefficient ( D F )
was influenced by total chloride content was almost
(as HCI and FeC12) in the strip solution. It shows that for O/A=.50, DFm
constant for OPAP (0.6 to 0.7-0.8) while it dramatically decreased for D 2 m A (2.3 to 0.2).
This suggests that OPAP and DZEHPA have different stripping mechanisms, the latter involving chloride presence in the iron(m) coordination sphere andior direct HCl extraction
by D2EHPA. Referring to the DZEHPA stripping isotherm given in Figure 4.20b, back-
extraaion apparently did not compromise the stripping efficiency of DZEHPA to as great an extent as tha of OPAP, at least at low O/Aphase ratios. Later in Section 4.3.6, an attempt
was made to quanti8 the relative proportion of unstripped iron with back-extracted chlonde
in each extractant.
[ 4-OPAP
+DZEHPA
Total C I (M)
Figure 4.23: Effect of aqueous chloride concentration on 0.95 F OPAP and 0.95 F DZEHPA stripping distribution coefficients at 20C; (OfA?).50;pe3'],,= 1 8.3 g/L (OPAP) and 13.8 g/L @2EHPA); 5 minutes contact time; no acid control). At an O/A phase ratio of 2.0. a similar negative effect was exhibited on D2EHPq dropping eficiency significantly frorn 68 to 38% when 6 N HCI-70 g / L iron(II) was used at 20C. However, OPAP behaviour notably reversed, this time slightly decreasing in stripping efficiency, f?om 36% to 3 1%, instead of slightly increasing, as it did at O/A=0.50. Refer to Table 4.10. Table 4.10: Equilibnum stripping performances of OPAP and DZEHPA at OIA=2.0; (0.95 F OPAP:20C, 50C; pe37 -21.6 g/L; 20 minutes contact time; no acid control); y(0.95 F D2EHPA: 20C; [Fe 7-p13.8 g/L,; 30 minutes contact time; no acid control). Extractant Strippant Temperature ](fi) CC) O 20 70 20 O 20 70 20 70 50
D r 4.2 1.2 1.1 0.9 0.9
D2EHPA
OPAP
Stripping OPAP with 6 N HCl-70 g/L i r o n o at 50C gave no improvement within experimental error as compared to 20C operation. This shows that temperature has little
eEect on OPAP stripping, nor is it expected to influence D2EHPA stripping based on this
and on published data on M..-A
@ernopoulos et aL 1996).
4.3.3.2 Impact o f FeCb presence on stripping isotherms
Far fiom enhancing stripping efficiency, the presence of FeC12 appears to have only minor
effects on the stripping of OPAP while dramatically decreasing that of DZEHPA To assess the overall influence of FeCll on stripping, isotherm changes relative to 6 N HC1 results were assessed in terms of w e shape-location, total iron build-up, and i r o n o retention.
Trends in curve c h ~ a c f e t i ~ ~ c s
Figure 4.24 plots OPAP and DZEHPA stripping isotherms using 6 N HCl strip feeds containing O g/L, 40 g/L, or 70 g/L iron(I1). Generally, curve characteristics improved for
OPAP and clearly worsened for D2EHP4 as the concentration of iron(II) increased. As strip
feed iron@) content increased, the OPAP curve height decreased and the lower end of the
curve shified to the left. A decreased curve height means that iron(III) build-up was
sacrificed, which is consistent with the OPAP i o n 0 stripping efficiency having decreased with an increase in iron@) concentration at higher O/Aphase ratios (Table 4.10). The lower end of the cume shifting to the le& indicates a decrease in i r o n o retention. As strip feed i r o n o content increased, the DZEHPA cume height also decreased, but the lower end of the
curve shified to the right.
The decreased cuwe height represents a more dramatic
compromise in iron(III) build-up, which is consistent with the pronounced negative effect that the presence of ironO had on DWIPA i r o n o stripping efficiency, given in Figure
4.21b,Figure 4.23, and Table 4.10. The lower end of the c w e shifting to the right signifies
that iron(m) retention increased, supporting the earlier postulation that back-extraction is more prominent with D2EHP4 especially at elevated FeCh levels. These trends will now be discussed in more quantitative terms.
Total Von builddp
Table 4.11 shows the amount of i r o n o present in the strip solutions following an equilibriurn contact at OfAphase ratio of 10 for d l stripping isotherms conducted with 6 N
HCI (initiai acid)-FeCh(0-70 g/L iron@)) strip feeds. Values at O/A=10are considered as
cmde estimates of the expected maximum i r o n o build-up. Firstly, with pure 6 N HCi,
0.95 F OPAP generated a greater build-up of i r o n 0 than did 1.25 F D2EHPA (45 g/L
versus 32 g/L i r o n o ) . Secondly, as the isotherm m e trends suggest, both OPAP and
D2EHPA showed decreased iron(III) build-up as the concentration of iron@) increased, with D2EHPA having the greater drop.
(a)
(b)
Figure 4.24: Enect of onCII) on stripping isotherms using 6 N HCI at 20C for: (a) 0.95 F OPAP;@) 1.25 F D2EHPA; (no acid wntrol); [~e~+],,,=21.6 &,21.3 glL (OPAP) and 19.5 g L , 20.1 g/L (DZEHPA). Table 4.11: ERect of i r o n o on i r o n o build-up in the strip solution at O/A=10; (20C; pe3f1,,,=2l.6 g L , 21.3 g/L(OPAP)and 19.5 g/L, 20.1 g/L (DZEHPA); no acid wntrol). Strip Feed 1(gn) PCl]. (N)
O
0.95 F OPAP
40
70
6 6 6
Sipped F e @ ) (fi) 1.25 F D2EHPA 32 45 27 41 38 26
Although there was an apparent sacrifice in iron(m) stripping eficiency and maximum iron@l) build-up as a result of iron(I1) presence, a suitable total iron build-up (in terms of total ferrous and ferric ion content) was nevertheless obtained. Table 4.12 shows that the
total iron build-up stripping 0.95 F OPAP with 6 N HCI-70 g / L iron(II) sip feed was
108 g/L. With 1.25 F DZEHPA and the same strip feed, the result was 96 g/LFe.
Table 4.12: Effect of iron@) on total iron(&m) build-up in the strip solution at O/A=10; (20C; ~e~7,.=21.6 g/L, 21.3 g/L(OPAP) and 19.5 g/L, 20.1 g L (DZEHPA); no acid control).
Strip Feed I(Bn) IHClIo (NI

O
Total Fe(II,III) Build-up (@) 0.95 F OPAP 1.25 F D2EHPA

45
32
Figure 4.25 shows the McCabe-Thiele analysis of each of the OPAP and DZEHPA stripping isotherms using 6 N HCC7O g& iron@) at 20C. The stpected iron(m) retention and engineering characteristics, i.e. number of stripping stages, were then estimated. As earlier
curve trends suggested, OPAP iron(m) retention favourably decreased, while that of
DEHPA increased with the presence of 70 g/L iron(II). OPAP retention decreased fiom
12.0 to 4.5 fl u o n o while D2EHPA retention increased from 5.0 to 8.0 g/L i r o n o as
s h o w in Figures 4.20 and 4.25. The higher retention atibuted to D2EHPA (even higher when an O/A=3.00 operating line is considered), may be due to the higher extent of iron(m)chloro cornplex back-extraction relative to OPAP,as was poshilated.
J
T
.
1
.
1
.
l
(a)
@)
Figure 4.25: Stripping isotherms usin 6 N HCI-70 g/L at 20C for: (a) 0.95 F OPAP; 5Ta0=21 -6g/L (OPAP) @) 1.25 F D2EJ3PA; F e and 19.5 g/L @2EHPA); no acid control; (LO = loaded organic; SF = strip feed; SL=strip solution; SO = stripped organic).
OPAP is prediaed to require 4 stripping stages in a continuous wunternirrent stripping circuit with an operating line of O/A=3.0. D2EHPA will also require 4 stages while
operating at a volumetric phase ratio of O/A=2.0. Compared to 6 N HCl stripping isotherms, given in Figure 4.20, the presence of FeCh adds on one stripping stage. Even so, this is still favourable when cornparhg to M2EHPA
4.3.4 Experimental verification of material balance findine: 'Moderate strength' acid
stripping
In Section 4.3.2, it was rdized that o n o build-up to or above 100 g/L,could not be
achieved with 6 N HCI strippant alone. In Section 4.3.3, a 6 N HC1-70 g/L ironm strip feed successfully achieved the required iron levels with OPAP, perfoming nearly as well with
D2EHPA However, this strip feed composition does not achieve the needed HCI balance
between stripping and pyrohydrolysis, according to a mass balance investigation that was conducted. Instead, a weaker, 'moderate strength' acid strip feed of a particular composition
was predicted to be more consistent with the desired zero net HCl discharge/production in a
recycled strip solution loop. Highlights of these simulation results, along w i t h experirnental
verification of the selected stnp feed composition, are reported below. balancing conditions and more detailed results are aven in Appendix C.
The material
The material balance analysis considered a conceptual flowsheet which introduced 'electroreductive' stripping as an iron concentration step between the solvent extraction stripping stage and pyrohydrolysiq the final step for iron by-product formation. The pertinent
conceptual flowsheet is given in Figure 2.6. A high concentration of FeC12 is maintained in

the HCl strip solution loop in order to pamit the concentration of ferrous and femc iron to
increase to econornically attractive levels, since yields when dealing with iron@I) done proved inadequate. Total i r o n o build-up is made possible by elearolytically treating the
strip solution directly, reducing a portion of the stripped iron(III) to non back-extractable
iron(II). This creates a favourable stripping equilibnum as the i r o n o product yield is 'removed' by reducing it t o i r o n o . Following the conventional and 'electro-reductive' stripping seps in each cycle, a portion of the stnp liquor is bled out for iron recovery by
pyrohydrolysis. Pyrohydrolysis also regeneratea HCI for make-up of the strip feed, which is then recharged with iron(III) upon contact with loaded organic to cornpiete one cycle.
4.3.4 1 Mass balance resulrs
Mass balance results indicated that any 6 N HCl(initia1 acid)-FeC12(0-70 gR, ~ e ~ strip + ) feed
would not translate into a build-up of 100 g/L or greater of total iron(II,m) while achieving a closed acid loop. Figure 4.26 summarizes the mass balance results given in Appendix C. According to these results, the total iron(4III) build-up in the strip solution is not actually expected to surpass 40 g/Lwhen a 6 N HCl(initia1 acid)-FeClz(O-70 glL F ~ ~ C strip ) feed is
used. Instead, a 3.38 N HCl strip feed is required to achieve both acid balance and mfficient
total iron(9m) build-up. The srip solution generated is predicted to contain 1.50 N HCI.
Cowequently, 6 N HCI was abandoned in favour of the 'moderate strength' stnp feed composition (3.38 N HC1-58.5 gR.Fe(II)-9.7 g/L Fe(III)).
3.38
3.88
4.38
4.88
5.38
5.88
[HQI m Stnp Feed (N)
Figure 4.26: HCl and total iron(lI,m) concentrations associated with a closed acid loop (refer to Appendix C mass balance conditions and assumptions). Figure 4.27 shows a conceptual flowsheet for a 200,000 tpy capacity zinc plant, which simulates an acid-balaaced circuit utilking the 3.38 N HCI strip feed. The total iron build-up requirement is met here.
SL:
44.74 g/L
Fc(m) 0s F c q
HCl
58.49
fi Fc(n)rr FeCt,
1.M N
SF:
9.74
fi Fe(m) u F e q
Figure 4.27: M a s balance flowsheet involving a closed acid loop iron SX integrated 200,000 tpy capacity zinc plant; (refer to Appendix C rnass balance conditions and assumptions); (HAL O/F=hot acid leach overflow; LO = loaded organic; Rec.Org=recycled organic; SF = strip feed; SL=stripsolution; redSL=reduced strip solution; SO = stripped organic).
Stripping isotherms at 20C were generated with 3.38 N Hel-58.5g L F m 9 . 7 glL F e 0 strip feed for 0.95 F OPAP and 1.25 F D2EHPA. Conditions were identical to previous stripping isothenn procedures. In addition, the OPAP O/A=10aqueous sip solution was titrated for fke acid content. In Sections 4.3.2 and 4.3.3, whether or not FeCl2 was present, problematic phase separation characteristics were observeci with 6 N HCl stripping. A t O/A phase ratio 1.O, separation
times were slow, on the order of 10 minutes or more. Even slower separation occurred with
higher OIA ratio% Le. greater than 1.0, at which some near stable emulsions formed. Based
on Figure 4.25, high OIA operating lines, 2.0 and 3 . 9 would be required which calls into serious question the technical feasibility of such an approach. In contrast, phase separation characteristics were very encouraging for the 'moderate strength' strip feed experiments. For both extnictants, the pnmary and secondary break times were only 60 seconds and 3.5 minutes, respectively, at phase ratio OlA=1.0. At higher OIA ratios, where relatively stable emulsions formed at 6 N HCl, secondary break times were less than 10 minutes. Phase disengagement characteristics improved significantly with lower HCI concentration strip feeds, improving in turn the technical feasibility of the stripping operation. Table 4.13 compares the simulation predictions of the strip feed and solution compositions that achieve acid balance, the data given in Figure 4.27, to OPAP 'moderate strength' stripping isotherm results. The experimental OPAP O/A=10strip solution result of 93.7 gR. total iron(9m) is close to both the build-up target of 100 g/L or greater and the simulation prediction of 103.2 g/L. Also, the experimental OPAP O/A=lO strip solution acidity
compares well with that of the simulation (1.80 N versus 1.50 N, respectively). The strip
feed composition using an operating line of O/A=4.0consists of 72.0 g/Ltotal iron acwrding to the McCabe-Thiele analysis given in Figure 4.28a. This value also compares reasonably to the simulation r w l t of 68.2 g/L. Considering the extent of agreement between the simulation and experimental data in Table 4.13, the closed loop iron build-up target appears to be technically altainable with 0.95 F OPAP.
Table 4.13 : Uass balance simulation-OPAP experimental results cornparison of strip solution compositions in 'moderate strength' acid stripping (20C).
Strip Feed Composition HCI F e 0 Fe@) Fem
Strip Solution Composition
(fi)
9.7
Simulation ; Experimentai
3.38 3.38'
1.50 44.7 58.5 103.2 68.2 9.7' 7 2 . 0 ' 1.80' 35.2 58.5 93.73 - initial stnp feed composition for isotherm test data from McCabe-Thiele diagram given in Figure 4.28a data from isothenn O/A=10sample titrations
(a) (gn)
58.5 58.5'
HCl
F e o Fe0 F
(a)
wu.

iin
.
0 Figure 4.28: Total i r o n o stripping isotherms using 'moderate strength' strip feed at 20C for: (a) 0.95F OPAP; @) 1.25 F D2EHPA; SF=3.38 N HCI, 58.5 g/L F e @ ) , 9.7 g/LF m ;[I?e37,=20.9 g/L, (OPAP)and 19.7 g L (D2EHPA); no acid wntrol; (LO = loaded organic; SF = strip feed; SL=strip solution; SO = stripped organic).
The expenmental and mass balance results compare well using OPAP, but poorly using
( 4
D2EHPA. Conceming 1.25 F D2EHP4 the flatness of the stripping isotherm given in
Figure 4.28b reflects how poorly the extractant is stripped with a moderate strength HCl solution. Figure 4.29 replots Figure 4.28 data in terms of i r o n o ody. Figure 4.29b shows a gain of only -7.0 g/L iron(III) by the strip solution fkom loaded D W I P k Despite the clearly supenor performance by OPAP, compared to D2EHPA when using the 'moderate strength' stnp feed, the former extractant nevertheless incurred a loss in i r o n o build-up relative to earlier 6 N HCl performance, as w e l l as continuing to yield a high
i r o n o retention. OPAP exhibiteci a 43% loss in maximum attainable build-up of b o n 0
based on O/A=10strip solution results (25.5 g/L versus 45 @L, respectively). However, with
OPAP, the strip solution gain in i r o n o is comparable to performance by 6 N HCl alone in
terms of McCabaThiele analysis which predicted 19.5 g/L and 2 0 . 5 g/L, respectively. In tenns of this latter criticai measure of performance, 'moderate strength' stripping appears to be as effective as stripping with 6 N HCl. T h i s suggests that 3.38 N HCl stripping power was
boosted by the presence of FeC12, in contrast to the 6 N HCl strip feeds. However, this
cornparison is being made between McCabe-Thiele diagrams (Figures 4.20a and 4.29a) that
are drawn at different operating line OfA ratios (O/A=3.00 and 4.00). With OPAP, the
observeci phase volume changes in stripping limit McCabe-Thiele diagram cornparisons to those drawn at the sarne operating line OIA slope. Considering this dong with the major findings, M e r mass balancing work is necessary as the original stripping performance assumption (that the strip solution gains 35 fi i r o n o every cycle) has to be adjusted to a
more representative value, e.g. on the order of 20 g/L i r o n o . This will help to tiirther
optimize the best simulation strip feed composition required for both acid balance and iron build-up.
(a)
(b)
Figure 4.29: I r o n o stripping isotherms using 'moderate strength' strip feed at 20C for: (a) 0.95 F OPAP;@) 1-25 F DZEHPA; SF=3.3 8 N HCl, 58.5 gR.Fe@), 9.7 glL F e @ ) ; pe3+],,,=20.9 g/L (OPAP) and 19.7 g/L (DEHPA); no acid controi; (LO = loaded organic; SF = strip feed; SL=stnp solution; SO = stripped organic).
4.3.5 2n2+and ~01% carry-over to strip solutions
The strip solutions from stripping kinetics tests conducted with 0.95 F OPAP and 0.95 F
DZEHPq reported in Sections 4.3.1 and 4.3.3, were analyzed for residual zinc and sulphate.
These results allowed for the examination of the zinc and sulphate cany-over to strip
soiutions &om the unscrubbed loaded extractants. In addition to comparing the extractants generaliy in ternis of carry-over, the &ects of strip feed acid strength (4 N and 6 N HCI) and
the presence of FeClz (30
fi and 70 g/L i r o n o ) on carry-over for each extractant was

studied. In terms of kinetics al1 zinc and sulphate carry-over, like i r o n o stripping, reached
equilibrium in less than 5 minutes contact tirne.

4.3.5.1 Catgwver using pure HU solution as ~ a p p a n t
The major findings observed under loading conditions discussed in Section 4.2.2, were that
OPAP co-extraaed less sulphate while DZEHPA co-extracted less zinc. These tendencies
were confirmed with the strip solution analysis results reported in Figure 4.30. The sulphate
carrysver w i t h D2EHPA is four times greater than that with OPAP. Arnounts of 2.10 g/L
and 0.50 f l SO? reprted to the 6 N HCI strippant om the extnictants, respdvely. The
zinc carrysver for OPAP is four times that of D2EHP4 however, levels are low relative to
mlphate. Arnounts of 160 pprn and 40 pprn 2n2' reported to the 6 N HCI strippant fkom the extractants, respectively. In terms of strip fed HCl strength, higher HCI concentration appeared to decrease zinc and sulphate caq-over to strip solutions firom loaded OPAP. Stripping OPAP with 4 N HCI and
6
N HCl strip feeds generated strip solutions containing 190 pprn and 160 pprn 2n2', respectively, and 560 ppm and 500 ppm , : O S respectively. With respect to D2EHPA, strip
feed strength had no effect on either zinc or sulphate carry-over.

4.3. S . 2 Effeco f Feu2on 2n2+anri S O cany-over ~
Figure 4.30 shows that increasing strip feed i r o n o concentration lowers zinc and sulphate
carry-over fiom loaded OPAP or D2EHPA dunng 6 N HCl stripping. Zinc wry-over was lowered by 70 g/L iron(II) om 40 pprn to 30 pprn 2n2+w i t h D2EHPA, and fiom 160 pprn to
110 pprn 2n2+with OPAP. Sulphate carrysver was lowered fkom 2.10 & to 1.74 g/L SO?
with D2EHPA and f i o m 500 pprn to 370 pprn SQ"
w i t h OPAP. These results are encuuraging for 'moderate strength acid stripping' in terms of zinc and sulphate carry-over minimization, since the strip feed FeC12 concentration of 58.5 g/L iron@) is high enough to have beneficial effects on reducing zinc and sulphate carry-over.
Figure 4.30: Zinc and sulphate cafcy-over to the sip solution fiom unscrubbed loaded organic at 20C: (a) zinc; @) sulphate; O/A=O. 50; ~e'+],sl8.3 g/L (0.95 F OPAP) and 13.8 g/L (0.95 F D2EHPA); no acid control.
4.3.6 C carry-over to organic phase
Like zinc and sulphate cany-over to stnp solutions, chloride back-extraction to the stripped organic phase, ultimately transfemng to the raffinate, is an equally intolerable aqueous
Stream contamination problem. Zinc and sulphate in the strip liquor compromise iron byproduct quality and hence saleability and chloride in the raffinate lowers z i r electrowinning ~
r o m acid and nonm e n t efficiency. For the test discussed in this section, stnpped samples f
acid control stripping isotherms were smbbed of chloride according to the scrubbing method developed by Demopoulos et al. (1996) for M2EHPk The isoacid isotherms were conducted at 20C with 0.95 F OPAP and 0.95 F D2EHPA at the usual O/A phase ratios.
Each O/A contact was mixed for 2 minutes, centrifuged, and then the strip solution was
titrateci for fiee acid. The sip solution acid level was adjusted w i t h concentrateci HCI, and
then re-contaded w i t h the same organic phase. T h i s cycle was repeated until free acid levels became constant at 6 N HCI. At this point of isoacid equilibnum, the organic phase was
sampled. For the non acid-controlled stripping tests, the organic sarnples were taken fiom
stripping isotherms that employed either 6 N HC1-40 g/L F e 0 or 3.38 N HC1-58.5 g L
Fe@)-9.7 g/L F e 0 sip feeds (Sections 4.3.3 and 4.3.4) with 0.95 F OPAP and 1.25 F
DEHPA.
Scrubbing of ~ W ~ ? d e f r stnpped ~ m organic samples
The M2EPA scrubbing procedure developed by Dernopoulos et al. (1996) for the removal
of back-extracted chloride from stripped organic samples called for consecutive contacts with
50 H2S04at 20C and O/A=.50. Three contacts were selected since 2 contacts sufficed
with MZEHPA After mking, the phases were then centrifuged in order to ensure ~ m p l e t e
phase separation. The generated scmb liquors fiom the same smbbed organic were
combined as a composite sample that was analyzed for Cl-. A secondary scrub liquor
generated fiom a subsequent single contact with 50 g/L H2S04 was separately sarnpled and analyzed to confinn that scrubbing was complete.
Notrcre of chloride cany-ovet io organic phase
HCl extraction was not the only source of choride carry-over. HCI as the exclusive source of chloride loading would be consistent with loading being independent of OIA ratio dunng isoacid conditions. That iq isoacid conditions would be expected to saturate the organic with the same concentration of HCI, regardless of O/A phase ratio. Instead, Figure 4.3 l a shows
that chloride loading increased with OIA during isoacid conditions, which suggests that
sulphate anions coordinated to loaded iron(III) were mchanged with chloride forming irono-chlorwrgano complexes. An increasing OIA ratio cornesponds t o an increased amount of unstripped i r o n o in the organic phase. More unstripped iron(IlI) means that more coordinated iron(III)-chloro complexes will exist at isoacid equilibrium. An increased
amount of coordinated Cl- means higher chloride loading.

&&actant cany-over cornparison
OPAP exhibited significantly lower chloride back-extraction than DZEHPA At an OIA
phase ratio of 1.0, OPAP back-exeaded less chionde than D2EHPA when either 6 N or
'moderate strength' sip feeds were used, as shown in Figure 4.3 1b. With a 6 N HC1-40g l L
F e 0 strip feed, 4.1 g/L and 20.4 g L Cl- were back-extracted onto OPAP and D2EHP4
respectively, and with a 3.38 N HCl-58.5 glL F e @ ) 9 . 7 g/LF e 0 strip feed, 0.7 g/L and
10.1 gfL
Cr were back-extracted, respectively. Therefore, cany-over tendencies favoured
'moderate strength' over 6 N HCl stripping. In the 'moderate strength' stripping case,
D2EHPA had greater chloride back-extraction than OPAP by a factor of 14.
0,IO
0.25
1.O0
0 . 9 % OPAP
(b)
1.2SFD2mPA
WA
(4
Figure 4.3 1: Chloride back-extraction during stripping: (a) phase ratio effect (20C; 6 N HCl equilibrium acidity); @) strip feed effct (20C; O/A=1.0; no acid control). Relative chtonde-iron(III) levels (on a molar basis) in stripped D2EHPA suggest a predominance of iron@I)-chloro complexes. T a b l e 4.14 shows that OPAP and DZEHPA differ drarnatically in this respect. A molar C l X e @ ) ratio of less than 1 for OPAP suggests minimal iron(m)-chloro presence in the extractant after stripping. T h i s reflects the low Cl-
transfer exhibited by OPAP, an attractive feature as the implied scrubbing measures would
not need to be as intensive as with D2EHPA or M2EHPA A ClFe(m) ratio greater than 1
for DZEHPA suggests the predominance of irono-chloro
species such as
FeC12'/FeCb0/FeC4; which were predicted to predorninate in the aqueous stnp phase amrding to Figure 2.5. This is consistent with DZEHPA i r o n o back-extradion being sensitive to high queous chloride background that was reported in Section 4.3.3, due to
FeCh and strong HCI presence. It is clear at this point that OPAP and DZEHPA stripping
mechanisms are different.
Table 4.14: Molar ratio of loaded C1'and ~ e in~stripped + OPAP and DZEHPA at 20C.
1 1
1
O/A
Stri~ Feed Com~osition 3.38 N HCI, 1 6 N HCI, 58.5 p/L F a ,9.7 g/L F e 0 40 p,/L Fe@) 0.95 F OPAP 1.25 F D2EHPA 0.95 F OPAP 1 1.25 F D2EHPA

4.3.7 Nitric acid stripping
Nitric acid stripping of loaded OPAP is expected to be poor based on previous D2EHPA performance (Van W e e r t et aL 1998) and the inherently we& stripping tend
(Sato et al. 1985).
e s of HN03
Ln order to confirm this, a stripping isotherm was
consti +ed for 4 N
H N a stripping of 20% v/o OPAP at 50C. Except for stripping operating temperature,
selection, and dosage, test conditions followed the same procedure as detailed for HCI stripping in Section 4.3.2. Strip solutions were analyzed for zinc and sulphate to monitor
h i s stripping testwork was done in order to rule out carry-over nom unscmbbed organic. T
the possibility of HN03 as an effective i r o n o stripping medium for OPAP. If nitric acid were to prove effective, then downstream autoclave hydrolysis could potentially be applied
(Shang and Van Weert 1993). The generated isotherm is compared with the 4 N HNC& isotherm data for 20% d o DZEHPA et 50C from the literature (Van Weert et aL 1998).
Although the quantities of OPAP and DZEHPA are not equd on a molar basis (0.53 F versus 0.62 F, respectively), 20% v/o OPAP was selected as loading capacities were expected to be similar after consideration of the loading limitations imposed on D2EHPA in a non acidneutralizing loading preparation.
With regard to phase disengagement, organic continuous sepmtion times were very favourable. For O/A phase ratios 1.O-10, primary and secondary break times were 1-2 minutes and 3-4 minutes, respectively. The organic phase was very clear exhibiting a dark
rich red-brown colour throughout al1 contacts and al1 final strip solutions exhibited only a
slight yellow tint. These observations alone suggest poor i r o n o stripping. Aqueous continuous contacts yielded similar clean separation, and only took 15 seconds. Consistent with the above observations, nitric acid was found to pooriy strip loaded OPAP at
50C. Results were comparable with those of D2EHPk As anticipated, 2% v/o (0.53
F)
OPAP gave the same loading capacity as 20% vlo (0.62 F) D2EHPA (11.3 g/L versus
11.5 g/L iron@), respectively). Figure 4.32 shows both the resulting OPAP and literature D2EHPA isotherms. Iron(IlI) build-up was very poor for both extractants. In terms of
highest available O/A contact sip solution results, maximum build-ups of only 6.4 g/L and
6.0 g/Li r o n o (DFw= 0.6) are expected for OPAP and D2EHPA, respectively. OPAP
iron@[) retention is expected to be greater than 5 g/L, slightly more than that expected for
D2EHPA T h i s is very poor considering that this represents approximately 50% of the
original OPAP or D2EHPA loading capacities.
11
0 20% d o D2EHPA
0 20%
v/o OPAP
Figure 4.32: Stripping isotherms using 4 N H N aa t 50C: ~d7,=11.3 g L (0.53 F OPAP) and 11.5 g/L (0.62 F DZE3IPA); no acid control; (D2EHPA data taken fiom Van Weert et aL 1998).
Low zinc and sulphate carry-over was exhibiteci by OPAP, using 4 N HN03, relative to
D2EHPA and OPAP stripping results with 6 N HCl. Table 4.15 makes this cornparison in
h i s difference tenns of the strip solution results generated at an O/A phase ratio of 0.50. T
may be attributed in part to the relative loading capacity differences of the extractants
employed, Le. 11 g/Lversus 20 g/L. Van Weert et aL (1998) found very high sulphate
transfer from 1 0 0 h v/o D2EHPA to H N a sip solutions (-1: 1 molar quantities), which
indicates that D2EHPA COsulphate in significant arnounts fiom HAL composition
aqueous feed. This was not the case for OPAP acwrding to Table 4.15. In ternis of O/A=10
stnp solution anaIysis, when stripping with 4 N HN03 at 50C, 2% v/o OPAP had optimal
c811yi)ver of 300 pprn 2n2+and 879 ppm SOZ-to the stnp solution.
Table 4.15: Zinc and sulphate carry-over to stnp solutions at 50C (O/A=.50).
Extractant
0.53 F OPAP 0.95 F OPAP
,
Strippant
znz+(ppm)
13 160 40
4NHN03
6 N HC1
SOT (ppm)
29 500
1.25FD2EHPA [
6 N HC1
2100
5. Conclusions and Recommendatioris

5. CONCLUSIONS AND RECOMMENDATIQNS
5.1 CONCLUSIONS
Iron(III) solvent extraction removal fiom synthetic zinc plant hot-acid-leach (HAL) solutions by OPAP (octylphenyl acid phosphate) and D2EHPA (di-(2-ethylhexy1)phosphoric
acid) was studied within the context of stripping with strong HCI to generate an iron chloride
rich feed fiom which a marketable downstream iron by-product can be produced, i.e. wastefiee iron removal. The major findings are as follows.
Solubilig and s t a b i t y
(1)
OPAP solubility-degradation levels in either aqueous loading or strip solutions were
excessive at SOC, but were found to be acceptable at arnbient temperature.

(2)
At 50C, DWIPA exhibited Iower aqueous solubility and l e s degradation than
OPAP. Therefore, it is the preferred extractant at 50C.
(3)
Organophosphoric extractants degrade more extensively in HCI strip solution than i n ZnS04-H2S04 raffinates. Aqueous iron(m>catalyzed ester hydrolysis of the extractants has been postulated as the degradation reaction.
&&action pcrfrmame und ~k+/(zfl,So/? seecfiMQ
(4)
OPAP (0.95 F) at 20C exhibited higher loading capacity than DZEHPA (1.25 F) at 50C when no neutnilization of the HAL aqueous feed was performed. OPAP was
found to be a stronger exfractant, having greater pH functionality than D2EHPA In terrns of uon(m) extraction kinetics and efficiency, OPAP loaded more iron(m) and
had faster extradion kinetics than D2EHPA. In terms of selectivity, OPAP coextracteci slightty more
zinc, but significantly less sulphate than D2EHPA OPAP
appears to be the most selective on record against sulphate co-extraction. Phase

disengagement was under 5 minutes for either extractant.
5. Conclusions and Recornmendations

(5)
Extraction with OPAP at 20C a h gave less sulphate co-extraction than at 50C while not significantly compromising ~ d + / ~selectivity n ~ + . For this reason, and the l e s pronounced degradation that occurred at 20C, al1 subsequent OPAP test work
was conducted under ambient conditions.
(6)
At 50C, although D2EHPA F ~ + / z ~ ' + selectivity was improved, the already signifiant sulphate co-actraction was enhanceci. However, extraction operation at
20C was not practical as DZEHPA loads i r o n o poorly under non-acid control
conditions. Loaded 1.25 F DZEHPA also showed stability problems as it was found to form a precipitate over time.
Sbipping performance and iron buildicp
( 7 )
Only ambient temperature stripping was wnsidered. Iron(III) build-up to or above

100 g/L could not be achieved with 6 N HCI alone. However, 6 N HCl-70 g/L iron(II)
strip feed was able to meet the desired strip uon target with both OPAP and D2EHPA.
(8)
The requirement of FeC12 presence in order to attain acceptable iron build-up calls for
the integration of an iron(III) reduction step between stripping and pyrohydrolysis.

(9)
Strip feed containhg 6 N HCl-70 g/L iron@) does not achieve the needed HCl balance between stripping and pyrohydrolysis according to a mass balance investigation that was conducted. Instead, a 'moderate strength' acid strip feed, of composition 3.38 N HC1-58.5 g/L Fe@)-9.7 glL F e o , was both predicted and confirmed experimentally with 0.95 F OPAP to acceptably attain both total iron(II,III) build-up and zero net acid dischargdproduction. Under these conditions, OPAP exhibited favourable phase separation characteristics and exceptionally low chloride back-extraction.
Scricbbing measuns
(10)
Loaded OPAP and DZERPA organic sarnples were effdvely saubbed of cosdracted zinc and sulphate using 0.82 N HCI. As for M2EHP4 0.5 M H2S04 efktively scnibbed chloride fiom stripped OPAP and D2EHPA organic samples.
5. Conclusions and Recommendations
5.2 RECOMMENDATIONS FOR FUTURE WORK
Sulubility and stability

(1)
The solubilized phosphorus content due to extractant aqueous sdubility and
degradation requires characterization for both OPAP and D2EHPA For a given aqueous sample, knowing the colorimetric spectnim (%VIS) for inorganic phosphate, POI*, and the ICP analysis remlt for total residual phosphorus, the
concentration of phosphorus which is present as solubilized phosphate ester can be

calculated by ciifference. Consequentiy, the extent o f solubility and degradation that occurred under each set of conditions could be quantitatively determined for each of
the contacted aqueous streams (washing, scrubbing, loading, or stripping).
Impurity C(Yf)hOVer
(2)
Organic samples fiom long-tenn degradation tests on both OPAP and D2EKPA
require scrubbing-anaiysis of 2 n 2 ' , worst-case carry-over levels.
SOI', andor Cr content in order to determine the
EjetrllCa*onperformartce
(3)
Extraction slope analysis should be performed in an attempt to elucidate OPAP and DZEHPA extraction mechanisms which consider zinc and sulphate co-extraction.
s b p p h g perfrmunee
(4)
The maximum i r o n o build-up produ& in strip solutions at various HCI strip
feed concentrations should be determined by performing consecutive contacts of the same strip solution with fieshly loaded OPAP or D2EHPA aliquots. Stripping slope
d y s i s should be conducted in an attempt to elucidate OPAP and D2EHPA stripping mechanisms.
5. Conclusions and Recommendations
Ele~lro~~ssisted sfnpping fechnology
(5)
The materiai balance perfonned as daailed in Appendix C should be revised w i t h an approximately 20 g/L b o n 0 cyclic gain in the strip solution loop. This would help
refine the predicted 'moderate strength' strip feed composition that gives a maximum iron(II,m) build-up while maintainhg an acid balance in the stnp solution loop. Experimentally, batch electrolytic tests evaluating various cost-effective electrode materials should be investigated. Matenal balances and a cost anaiysis should be generated considering galvanic stripping in place of 'electro-assisted', i.e. electro-reductive, stripping as an iron concentration step between solvent extraction stripping and pyrohydrolysis. Zinc dust or iron scrap could be used as alternatives to or in combination with iron(II) chloride. Expenmentally, addition to either the stripping emulsions or separated strip solutions should be wnsidered.
(6)
DmultSfrem on by-pr& et production
(7)
ther iron by-product routes suggested in Chapter 2 should be exploreci.
References
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Ritcey, G.M., Ashbrook kW., and Lucas, B . H . , CA4Bulletin, January (1975) 111. Ritcey, G.M. and Ashbrook, A W., Solvent fiiraction: Principles and AppIicaz?ons to Proces MetolIwgy, Purt 1, Elsevier, Amsterdam, Netherlands (1984) 60. Ritcey, G. M., in Iron Conbol in HjdkornetalIwgy, J E . Dutrizac and AJ. Monhemius (editors), Ellis Horwwd, Chichester, England (1986) 247.
Riveros, P A ,Dutrizac, J.E., Benguerel, E., and Houlachi, G., Mineral Proces. &tr. Metall. Rev. 18 (1998) 105. in EPD Congress 1990, D.R Gaskell (editor), TMS, Warrendale, PA ( 1990) Robins, R G., 93. Robins, KG., Twidwell, L.G., Dahnke, DK, McGrath, S.F., and Khoe, G.H, in EPD Congress 1991, D R Gaskell (editor), TMS,Warrendale, PA (1% 1) 3.
Rolia, E. and Dutrizac, J . E . , C m Metall. Q. 23 (1984) 159. Rosato, L.L and Agnew, M.J., in Iron Control and Disposal, J.E. D u t r i z a c and G.B. Hams (editors), C M Montreal (1996) 77.
Sahu, K.K. and Das, RP., Met T r m . B. 28B (1997) 181.
Sato,
T., Nakamura, T . ,and Ikeno, M., Hy&orne&IZwgy 15(1985) 209.
Shang, Y.and Van Weert, G., H@omefaIIuqp 33 ( 1 993) 273.
Shriver, D.F., Atkins, P.W., and Langford, CH.,Inorganic Chemistry, W.H. Freeman & Co., New York (1990). Silcock. H.l.(editor), SalubiZities of Inorgrmic and Organzc Compamcis,Volume 3 : Tenuqy and Multicomponent Systems o f Inorganic Substances, Pergamon Press, Oxford
(1979) 566,570,803.
References
Sillen, L.G.and MarteIl, A.E., Stability Comcmts o f Metal-Ion Complexes, The Chemical Society, Burlington House, London (1964) 53-4, 185,240.
Sillen, L.G. and Martell, M., Stability Constmts of Met&Ion CompIexes: Supplement No. 1, The Chemical Society, Burlington House, London (197 1) 22, 110.
Smith,RM. and MarteIl, AE., Critical Stability Coltsfmfcr,Vol.3, Plenum Press,New York
(1976) 360.
Smith, RM. and Marteil, AE., Criticai Srabiizq Comants, Vol. 4, Plenum Press,New York (1977) 7, 57, 83.
Sohrent Extraction Workrhp 1997, Banff, Alberta, October (1997).
Tabor,J., personal communication, Albright & Wilson Americas, Virginia 1999.

Van Weert, G., personal communication, Oretome, Ontario 1997. Van Weert, G., van Sandwijk, T., and Hogeweg, P., in EPD Congress 1998, TMS, Warrendale, PA (1 998) 245. Vasil'ev, V.P., Rus. J of Inorg. Chemistry 7 (1962)924.
Weininger, S.J. and Stermitz, F.R, Orgmc Chemistry, Academic Press, Orlando (1984)
573.
Wilkins, RG., Kinetics mid Mechanisnt o f Reactiom o f Trmrftion Metd Complexes, VCH Publishers, New York (199 1).
Y u ,S. and Chen, J., HyCiometaiIurgy 22 (1989) 267.
APPENDIX A
MODIF'IED FIWE ACII) TITRATION METHODOLOGY
Accurate d y s i s of free acid (H2S04 or HCl) concentration in either strong H2SOc

Fe@O4&ZnSOqw
or strong HCl-FeC13(-FeC12)(a selutions is invaluable to the zinc
indu-.
Analysis by simple neutralization with an alkaline titrant alone is very problernatic.
i t h NaOH proves ineffective as neutrdization raises the analyte pH For example, titrating w
above 4, causing result-distorthg i r m o hydrolysis to occur. The method which employs

Na2Ca as the titrant, iron(I) reduction with KI, and a methyl orange indicator (Kolthoff
and Sandell 1947) has been used on-site in certain zinc plants. However, in the lab, this approach yielded enormous error due to persistent hydrolysis that occurred duMg acid neutralization. Since the error was not reproducible (varying between 5.20% at al1 acid levels), a strialy followed calibration methodology could not effectively correct for this hydrolysis. Consequently, a method utilizing a cornplexing agent was wnsidered.
u t r i z a c (1984) developed an analytical method that employed EDTA as a Rolia and D

complexing agent. The principle behind this method is that a prepared MgEDTA solution is added in solution with the aliquot pnor to neutralization. The M~EDTA~' complex very favourably exchanges Mg for the hydrolyzable metals (Fe3+,
zn23that are present in the
analyte. This prevents any acid-producing metal hydrolysis that consumes titrant (0.1 N NaOH) as it is added nom occurring, thus avoiding erroneous results. However, problems were encountered in applying this procedure to the experimental samples of interest, regardless of metal-acid medium. Hence, modifications to this methodology were necessary.
A.1 FREE ACID DETERMINATION IN STRONG H2SOcF~(S04~-~SOqw
Diflculties with the MgEDTA method
When applying the method by Rolia and Dutrizac (1984), it was found that the suggested endpoint pH (6.3) was too high for the samples in this work as significant hydrolysis occurred. Titration results of prepared standards also overshot the known preparation concentrations by
5-20% in repeated atempts (data not shown). As well, minor inconsistencies were observeci
om day-to-day. The required endpoint pH for any given standard was sensitive to slight
compositional variations in the different MgEDTA solution batches, al1 of which had been
prepared according to the same procedure. In addition, even though pH electrode calibration
was done daily, the standardized endpoint pH value varied slightly each day, even though the
same MgEDTA batch and other reagents were used.
Standards were prepared containhg a range of compositions simulating the expected experimental samples. Table A l shows the prepsrations for 250 mL batch pairs of H2S04only ('A') and H2SQ-F~(SO4~-ZnSO~~-containing ('AFZ') standards. Titration of the
'A'-type standards gave an accurate estimate of the acid content of their 'AFZ' counterpart
solutions, and via their cornparison, the degree of hydrolysis could be determined. The
'AFZ'-type standards d l contained 25 g/L iron(m) (as Fq(SO&) and 90 g & 2 n 2 ' (as
ZnSO4). Al1 standards contained H2S04at concentrations of 1 gR, 1 0 g/L, 25 g/L, 50 g/L,
Table A. 1: Preparation of 250 mL H2S04-F(SO)3-ZnS0 standards ('A'=acid only; 'AFZ'=acid + i r o n o and zinc sulphates).
Standard
#/type 1A
HzSO~ &SOd
(B)
0.259 0.259 2.59 1
(%w/w)
96.5 96.5 96.5 96.5 96.5
1AFZ
2A 2AFZ
3A
3AFZ
2.591 6.477 6.477
9 6 . 5
Analysis by pH inflection point q l o r e d

The original method described by Rolia and Dutrizac (1984)determined the quivalence point
via titrant addition to a predetermined endpoint pH, Le. pH 6.3. Due to the problems
described above, the endpoint approach was ternporarily abandoneci in favour of considering
Aopendix A.
infiection point methodology.
T h i s latter method involves the use of first denvative
inflections (dope values) t o determine the equivalence point.

An automatic titrator was used to execute al1 titrations. Table A2 shows the titration results.
The idection point approach was also found to yield exaggerated results (4 to 17% above the prepared acid concentrations for 'AFZ' samples containhg 2 25 g/L H2S04). Again, the
inflection point results were distorted by the partial metal hydrolysis that occurred. A
correction fhctor was applied by subtracting the titrant volume difference (AFZ-A) at 1 g/L H2S04(0.987 mL) from al1 other 'AFZ' titrant volumes. ln tems of analyzed HzSO4 this
correcteci al1 'AFZ' sample results to within fi% of the corresponding 'A' samples.
Therefore, this correction factor approach appeared to be effective when 1 gR. H2S04 standards ('AFZ' and 'A') were used as blanks.
+
1
Table A.2: Titration analysis of H2S04-Fa(S04)3-ZnS0qa standards ('A'=acid only; 'AFZ'=acid + ironCm) and zinc sulphates).
Standard 0 . 1 O O 6 N Deviation 1 A&%A 1 m2S04] no dlflerence app(ying correction correction
Deviation applying correction
1 Equivalence
inierpo2aied
PH
10t .8 +9 1.394 104.5 +2.6 used; 1.00 mL was used in al1 other titrations
6.32
Refemng to Table A2, interpolation of titrator data for the same tests determined a cornmon endpoint pH of -5.75 for al1 standards except standard 6AFZ, which used a different aliquot volume (0.75 mT, versus 1.00 mL). T h i s cornmon endpoint pH is considerably less than the
pH 6.3 value suggested by Rolia and Dutrizac (1984). Not only does this c o h that
hydrolysis actually did occur in previous AFZ titrations to endpoint pH 6.3, but more
importantly it suggests that the endpoint pH setpoint is sensitive to analyte preparation. Interestingly, the literature value of pH 6.3 is better suited to the analyte preparation involving
a 0.75 mL aliquot, as indicated in Table AZ. Different aliquot volumes create substantially
+ aliquot + &O) when considenng different titration solution matrices (-120 mL:M~EDTA~the high metai salt content of the aliquots.
Analysis by en@oin?pH revisjteik Aduptotion ofthe MgEDTA method
Although the blank-subtraction approach above proved effective, the simpler endpoint method was adopted where a daily standardization of the endpoint pH setpoint was required. Standardization not only determined the endpoint pHP, but also corrected for pH caibration variations *~ among batches. Applying this procedure to the method of emor and F ~ ~ E D T A Rolia and Dutrizac (1984) proved very effective.
The standardization involved the
preparation and use of one 'AFZ7-type standard (solution A) of composition comparable to the experimental samples of interest. A second 'AFZ7-type standard (solution B), also of comparable composition to experimental samples, was prepared and used to validate the
standardization with solution A The acid levels of solutions A and B should be different, representing upper and lower lirnits of the range in which the experimental sampies fall. A
detailed procedure follows.

Methodology for free acid determination in &SO4-F~(SO4h-ZnSOqW samples
T%r(Eabon procedure
(1)
(2)
pour 50 mL of M~EDTA'~ solution into 150 mL beaker equipped with a magnetic stimng bar pipet 1.O0 mL of sample into same beaker mount beaker with solution in auto-titration setup and commence stirring dilute with distilleci water to 120 mL mark on beaker @y eye) then perform ' ~ ~ d i ~ * oor o 'simple n ' me~~tlrement'
(3)
(4)
(5)
(1)
prepare 2 metal-containing solutions with known, but dissirnilar acid concentrations
i) label the solutions A and B arbitrarily ii) both solutions should resemble the matrix and cover the acid concentration range of your samples use solution A as your standardization analyte and prepare the titration solution as in
the 'titrathprocechrre' above
set titfator to allow for a manual shutdown for this titraiion calculate the amount of 0.1 N NaOH needed to neutraiize analyte solutions A and B then press RUN to start auto-titrator feeding 0.1 N NaOH to solution A record the exact solution pH value at which the calculated titrant volume has been added
press STOP to end standardization titration (manual shutdown)

program the titrator by setting the pH endpoint to the recorded value and enable
automatic predose to a set pH value (below endpoint pH - high enough to advance the overall titration efficiently, but low enough to avoid overshooting of the endpoint) now use solution B to verify that standardizationjust perfonned as valid follow the 'tifrationprucedicre ' above using solution B as the analyte solution then follow 'sampie memurement as detailed below the d e t d n e d acid concentration should equal the known acid concentration
i) if m t equal:
-redo the standardization with solutions A and B
ii) ifequal:
-this confirms that the standardization was properly performed

mth solution A
-enmental
samples can now be analyzed by following 'titration
procehre ' (above), then 'sampie meanrrentent' (below)

Snmple measutement
(1) (2)
set to pertinent stored ENDPOINT methodology
press RUN to add 0.1 N NaOH Mrant autornatically following automatic shut-oe the total volume added to reach end-point is printed calculate the acid concentration
(3) (4)
A.2 FREE ACID DETERMINATION I N STRONG HCEFeC+FeC1&a
Presumably, the procedure that was adapted in Appendix A 1 for strong H2S04-F~(S0&ZnSOyw solution samples should be as successful with strong HCl-FeC13(-FeC12)(w solutions. However, attempts with the chioride medium samples introduced considerable complications. Consequently, analysis by pH inflection point was pursued and was found to be effective when a calibration procedure was implemented. Roblems with the adupted en@ointpH mefliod Applying the adapted method of Appendix A l to these solutions caused two serious problems.
Firstly, aliquots of 1.00 mL were found to sait-out EDTA upon mixing,
dramatically distorthg the results by removing the needed complexing agent out of solution.
This also caused a gradua1 rise in pH throughout the analysis, due to M~EDTA~' being exposed to relatively greater acid levels ( 2 6 N HCI) here than with the prior AFZ samples a s still rising, (0.5-1 M HzS04). When 0.100 mL aliquots were involved, the pH reading w
but much more s l o w l y with no appreciable saltingsut effects. However, at least 20 minutes
was requiied to have a stabilized pH reading for the (MgEDTA+aliquot+water) analyte
before each titration was commenced. Even after resolving the pH1MgEDTA stability issue, by using an smafler aliquot, a second problem rendered the endpoint method altogether ineffective. Due to the very high
H*
activity sensitivity to Fe(II,IIt)CIV-HCI compositional variations f i o m sarnple t o sample,

there was no cornmon endpoint pH. Instead, the endpoint pH varied by up to single units of
pH fiom sample to ample. This is in clear contrast to the consistent endpoint pH obtained
by sulphate-based @2SO4-Fa(S04h-ZnSOqa) samples at al1 'AFZ' compositions.
Development o f a pH infection point d o d

An inflection point method involving a calibration procedure was found efktive. Modifications lirniting saltingsut and initial pH instability problems were applied, these being: (i) taking a 0.100 rnL aliquot; (ii) allowing 20 minutes for the analyte solution pH to
stabilize prior to comrnencing the titration An effective shortait to the latter was used which
avoided the otherwise long waiting time per sample prior to analysis.
T h i s entailed
consistently mixing the (M@DTA+aliquot+water) analyte for 3 minutes (timed) before
starting the titrator which was set at fixed puameters for al1 samples. This way, the rising
pH behaviour due to instability persisted into the analysiq but was mnsistent for each sarnple
since a specific p r o d u r e was strictly followed. A correction factor was therefore applicable which correcteci for the excess titrant addition. In practice, the titrant volume result was
correcteci by either multiplying by 0.986, or equivalently subtracting 0.28 mL. It was not
necessary to determine the correction factor daily, but this was still verified periodically.
Instead of an endpoint pH setting as in part Appendix Al, an infiection point reject slope
setting w a s required. The inflection point approach proved advantageous since it operated
independently of cornpositional variations. A calibration procedure to determine the dope

seting was developed and conducted daily. It was found that the setting must be a minimal
and measurable slope, e.g. value -25, in order to maximize sensitivity thereby avoiding the partial metal hydrolysis that results with a more mature infiection point. No predose was used as very slow and consistent addition ensured reproducible results. Othenvise, a similar procedure to that in Appendix A 1 was followed which again involved 2 standards, A and B.
A detailed procedure follows.
Methodology for free acid determination in HCLFea(-FeCl&N samples

~ f r a t i o procedrrre n
(1)
(2)
pour 50 mL of M~EDTA"solution into 150 mL beaker equipped with a magnetic

stimng bar pipet 0.100 mL of analyte into same beaker
mount beaker with solution in auto-titraion setup and commence stimng
(3)
(4)
dilute with distilled water to 120 mL mark on beaker @y eye)

then perform 'caIibtafrafron ' or 'scanpIe meaiwement'
(5)
Gdibration
(1)
prepare 2 metal-containing solutions with known, but dissimilar acid concentrations i) label the solutions A and B arbitrarily
ii) both solutions should resemble the matrix and cover the acid concentration range
of your samples
(2)
use solution A as your calibration analyte and prepare the titration solution as in the
'titrdon procedure' above
set titrator to INFLECTION POINT mode maxirnize titrator sensitivity by setting a minimal inflection point reject slope, e.g. 25 calculate the amount of 0.1 N NaOH needed to neutralize analyte solutions A and B then press RUN to start auto-titrator feeding 0.1 N NaOH to solution A once the idection point is passed, the titrator stops autornatically and pnnts the result record the exact titrant volume added to attain the inflection point; calculate the acid concentration
the determined acid concentration should equal the known acid concentration for
solution A: i) if a equal: redo the calibntion with solution A at a different slope, e.g $25
ii) if equal:
- follow the 'titrationprocedure ' above using solution B as analyte
- follow 'smnplememirement below using the same settings as for A
the determined acid concentration should equal the known acid concentration for
solution B: i) if
equal: -redo the calibration with solutions A & B at a different slope setting
ii) if qual:
- this c o n f i s that the calibration was properly performed with

solution A
- experimental samples can now be analyzed by following 'titration

procechire ' (above), then ' m p l e memirement' (below) S<rmplemrasurement
(1)
set to pertinent storeci INFLECTION POINT methodology
(2)
press RUN to add 0.1 N NaOH titrant automatically

following automatic shut-ofS the total volume added to reach inflection point is printed calculate the acid concentration
(3) (4)
NB. no predose was programmeci as slow and consistent operation were found to be
conducive to good reproducibility
The purpose of this section is to attempt to postulate a theory to explain sulphate carry-over
via thermodynamics (stability constant analysis) and kinetic considerations of anion
H S -O ,; , OR, and ~ 0 4 % . The complexation with i r o n o . The anions of interest are S O ~ ~

fnst two anions represent the constituents of the industrial aqueous feed of interest, while the
latter is used to predict RtPO f (extractant) behaviour.
Work with NED (Lakshmanan et d 1996) showed that m04 as a co-stripping agent has proven to be eEkctive in removing i r o n o from the extractant. This implies that the Fe(IlI)-
PO^^ cornplex has p a t e r stability than F~(III)-so~Z' or FeO-HSO[

analysis. Section B.4 deals with ligand substitution kinetics.
during extraction. To
ven@ this reasoning on a thermodynamic basis, Sections B. 1-B.3 deal with stability constant
B . 1 STABIUTY CONSTANT DATA Table B. 1 lists the stability constant expressions for the equilibria of interest.
Table B. 1: Equilibria in the aqueous system F~'-OK-SO&PO~~.
ErtraCnoon condftions
The conditions at which solvent extraction loading occurs involve a temperature of 50C and molar ionic strengths ( I J of 33.5 M (0.25 M F4(S04b) and 7.5 M (O. 50 M Fe(S04h). The latter ionic strength is an exaggeration in order to test the limit of the Debye-Huckel-type equation used to determine P3pK and, as weli., to better represent the aqueous feed which also
includes 1.5 M ZnSOl and 0.5-0.75M H2S04.

Stqs involved in calculating sability constants
The first step used was the Helgeson Extrapolation (1967) to convert B0298K to P 0 3 z K for each cornplex. Table B.2 summarizes the stability constants and thermodynamic data that were selected for this treatment. Gaps exist in the irono-phosphato section due to the limited availability or existence of this data. The thermodynamic properties were found from various authors (Smith rmd Martel1 (1976-7), SilIen mtd Mirtell (1964, 1971), Hog/elldl (1982),
Kotrly und Sucha (1985), Bamer and Scheuennmt (1987), Naurnov et al. (1974), Robins et
al. (1991), Robinv (1990), Khoe d R o b z n s (1988), andFilippou et al. (1995)). Note that the
fiee energy, enthalpy, and entropy change values were reported in tenns of formation. This necessitated the use of the sarne properties for the reactant ion species so that epilibrium
values could be calculated by using Equation B.1.
These ~lcuated equilibnum
thermodynamic values are s h o w in Table B .3.
The b parameters for two ion@)-phosphato complexes were determineci amrding to

Vasii'ev (1962). The other b parameters were found h m Filippou et aL (1995). The DebyeHuckel constant,
&pK,
was detennined using water dielectric constant and density data at

The Vasil'ev treatment conchdes with
P 0 3 a ~being
50C taken fiom Lide (1991-2).
converted to f33=K at L= 3.75 and 7.5.
Table B .2: Selected thermodynamic data for the aqueous system F~~+-OE-SO&PO?.
b tenn
0.277 0.652 1.049 1.249 0.492
11.81 [O] 2 2 . 3 [O] 30 P l 34.4 [O] 25.1 [O] 4.04 [O] 5.38 [O] O 1.78 [0.15] 0 131 22.67[O] 19.5 [3] 1 0 . 1 [O] 8.30 [O.45] 8.13 [3] 13.18 [?] 1 1.40 [O.11 4.20[O] 3.47 [0.45] 3.61 [3] 4.9 [?]
Data taken fiom Smith and Martel1 (19767), Sillen and Martell (1964, 1 9 7 1 ) , Hogfeldt (1982), Kotrly and Sucha ( 1 9 8 5 ) , Bamer and Scheuerman ( 1 9 8 7 ) , Naumov et a l .( 1 9 7 4 ) , Robins et al, (199l ) , Robins (1990), Xhoe and Robins (1988),and Filippou et a l . (1995).
Table B.3 : Calculation of equilibriurn thermodynamic data.
B.3 GENERATED STABILITY CONSTANT FINDINGS
The calculated stability constants are tabulated in Table B.4. The hydroxo-iron(m)
complexes are clearly the moa stable amongst the three anions studied in terms of thermodynamics. However, the extremely Iow pH of interest (in extraction operation: 0.50.75 M H2SO4)in this work render the hydroxo complexes less favourable than the sulphato
complexes, as illustrated in the iron(m) speciation diagram given in Figure 2.4. Although, theoretically, it would be possible to obtain rnixed complexes because substitution reactions occur in a stepwise fashion. complexes cannot be nile out. Thermodynamically, iron(m)-inorganic phosphates form stronger complexes than su1phates. Iron@I)-phosphato complexes are s h o w to have stability constants (logfi&) between 10
and 20 while those of iron(m>sulphato complexes range oniy fiom O to 3. Figure B. 1 shows
Therefore, the presence of hydroxo-sulphato-irono
the phosphato complexes maintaining this higher stability relative to sulphato complexes
from infinite dilution to L=7.5 M. Stability actuaiiy decreases as molar ionic strength &)
increases, but appears to level off for al1 complexes.
Table B.4: Calculated stability constants.
Figure B.1: Stability constants as a bction of rnolar ionic strength.
Having established that iron(m) forms stronger complexes with inorganic phosphates than
with sulphateq relative organic phosphate complexation stability with iron(II[) was
considered in terms of a iogB0298~ estimation for Fe(IQD2EHPA transition metal serieq which includes F e @ ) ,
Figure B.2 plots
a funetion of metal center radius. The relationship is linear for both 1' row logp0298~as
and the rare-earth series, or lanthanides, in complexes with inorganic and organic phosphate,
PO^* and D2EHP4 respdvely.
Only trivalent species were considered, making this essentially a stability constant versus
charge density relationship. Linear regression analysis gives almost identical slope values
(-6.8) and good linearity (0.99).
The stability constant for Feo-D2EHPA at 298K
(logpomK)WU found by extrapolation to be 7.04. Although, this value was not adjusted for higher temperature and ionic strength, when compared to the first column of data in Table B.4, its magnitude indicates high complex stability relative to sulphato complexes. Here, inorganic phosphate proves to be a simple, yet effective indicator to mode1 organic phosphate, and hence extractant, complexation.
0.000
0.200
0.400 0.600 0.800 Metal(III) Radius (A)
1.000
1,200
Figure B.2:Estimation of the stability constant for F e ( ' D 2 E H P A at infinite dilution (data taken from Guseva et al. 1972).
8.4 LIGAND SUBSTITUTION KINETICS
A thermodynamically stable i r o n o complex does not ensure kinetic inertness which

warrants a kinetic investigation into iron(III) coordination. Do the kinetics follow the same order as thennodynamic indications? Sulphate CO-extractionmay be explaineci by a slow
(and consequently incomplete) exchange of sulphate/bisulfate ligands fiom the i r o n o
coordination sphere with extractant molecules during loading. Also, why are iron(IiI) and zinc extraction kinetics different? Dssociative ligand exchange Ligand substitution reactions are classified as either dissociative, interchange, or associative
mechanisms (Basolo and Johnson 1986). The dissociative mechanism is a unimolecular,
fustarder mechanism involving the cleavage (bond-breaking) of a metal-ligand bond to
i t h reduced coordination number. produce an intermediate w
Subsequently, an entenng
ligand associates with the metai-center. Birus et al. (1993) provide anation kinetic evidence suggesting that i r o n o operates by a dissociative mechanism. Suiphate complexation with i r o n o generated a positive change in activation entropy (+75 J/mol/K). This implies an
increased number of independent species in the theoreticai transition state pdL5+L1, which
is consistent with a dissociative mechanisrn (Shriver et al. 1990).

Zinc eYtr(LCllr-onkr'netics
Coordination behaviour cm explain the dissimilar extraction kinetics exhibited by ~ e and ~ + 2n2' ions. Going from lefl to right in the first row transition metal series, dissociative mechanistic character inaeases. In the case of zinc, located at the right-most end of this
series, dissociative ligand substitution is enswed by the inaccessibility of an entering ligand
on a 2nZC odahedron due t o al1 six coordination sites and al1 C3(syrnmetry) axes sites beinp
occupied by filled dsrbitals which repel the inwming base electron density (Henderson
1993). This explains why 2n2+coordination involves more s and p orbital overlap than does
~e~~ and is likely the cause of the kinetic differences existing between the two metals ions.
Sulphate cu-exfraction
As discussed in Section 4.2.2.4, steric effects can explain why OPAP co-extracts less
sulphate than doe DEHPA The greater bulkiness of the former should givo a more favourable dissociaiive rate.
Inotgmic phosphate as a mudel/or organophosphorus exttactant
Inorganic
PO^^ is a reasonable mode1 for organic phosphate in tems of kinetics, i.e.
steric
differences do not hinder kinetics. Although organophosphorus extractants are not chelates,
they can coordinate iron@I) in a bidentate marner, via one hydroxyl covalent bond and one
phosphonyl oxygen coordinate bond per extractant molecule. As mentioned in Section

4.2.3.2, the 'chelate' effect can therefore be argued to occur. Kinetically, this is also
advantageous. That is, once one end of the exractant 'chelate' attaches to iron(ICI), it is highly probable that the other end will attach next. This 'steric acceleration' logically increases the rate of reaction. It appears reasonable to state that organophosphorus extractants should have similar or greater kinetics relative to inorganic phosphate due to
steric eEects, therefore making them comparable.
Kin& findings incornpletc
In tems of thermodynamics inorganic and organic phosphates were found to form more
stable complexes with iron(?II) than sulphate/bisulphate does with i r o n o .
Having
established thiq a determination of how the kinetics behave was atternpted. Mentioned above, a positive change in activation entropy describing the kinetics of irono-sulphate anation is evidence supporting the dissociative mechanistic pathway. T h i s is consistent with the lower sulphate CO-extraction by di-OPAP as mrnpared to DWIPA for the reason that the
bulkier substmients of the former are conducive to higher relative sulphate lability on
i r o n 0 , as discussed in Section 4.2.2.4. However, there is an absence of any backward iron(IIK)-ligand exchange reaction rate constants (ks) in the literature. Consequently, a treatment as done by Benguerel (1991) was not possible where k$kb was used to calculate 'pseudo' or 'praaical' equilibnum constants on a kinetics basiq firom which a speciation distribution diagram could be generated. Therefore, a cornparison of the relative labilities of sulphate and extractants with respect to an i r o n o center aumot be quantined a t this point.
CONCEPTUAL INTEGRATED IRON SX-ZINC PROCESS FLOWSHEET
The conceptual integration of electro-sssisted stripping with iron solvent extraction in an RLE process was investigated. The feasibility of this integration was evaluated in terms of mass balances, electrochemical data, and a preliminary operating cost analysis.
C.1 MATERIAL BALANCES
As a preliminary process design investigation, matenal balances were developed to
determine whether the conceptual FeSX-Zinc Process flowsheet was viable in terms of engineering alone. A major stumbling block for the flowsheet was the question of achieving
an acid mass balance in the stripping-pyrohydrolysis aqueous strip Stream loop. Ideally, a
closed acid loop is desired while maintaining an adequately concentrated total iron strip solution (NO0 gR, Fe(II,III)) dong with a sufficiently strong strip feed make-up. Chosen conditions and assumptions
Each balance cornmenced with the inputting of a desired strip solution acid concentration.
An iterative approach was then followed until al1 compositions became constant coinciding
with a zero acid discharge or deficit.

-conditions
200,000tpy Zn metal plant capacity
zinc concentrate composition: 52% Zn, 7% Fe (4.39 tph hematite production)

153.7rn3h~&0/F
extraction A/O = 1.O stripping O/A = 1.75

87.8 m3/h strip solution
-assumptiots
smbbing procedures, membrane(s), or lime neutdization were not considered minor losses were ignored, e.g 4% HCI loss during (spray roaster) pyrohydrolysis loaded and recycled organic iron concentrations were 25 g/Land 5 & respectively
strip feed aiways increased by 35 g/L
30 glL
upon stripping.
in the strip liquor was always electro-reduced to Fe@), which translates to
aa acid conce~itiatian incrase of 0.54 N HCI (dculaed)

electro-reduced strip liquor stream fiaction going to pyrohydrolysis was the amount that generated 4.3 9 tph hematite pyrohydrolysis produced 6 N HCl Equations C. 1-C.4 are the chemical reactions considered in the calculations for Fe(LI,III) and
HC1 deportment dong the various streams. The outcorne is comprised of the Figures C. 1-C.6
and 4.27 flowsheets which simulate an acid balanced circuit. Figure 4.27 was the mass
balance which provided optimal results.
LO:
2 . 5 gn
SL:
42.91 gCL
2.00 N
F
HCI
FeCf,
SF:
7 9 1 g/L Fe@) as FcCh
1
87.8
87.81m'h
47.40 g/i, F m u F&l1
3.88N
HCI
0.0 m'h bleui 6.00 N HC1
6.00 N HCI
HYDROLYSIS
Figure C.1: Mass-balance conditions giving closed acid loop with 3.88 N HCI stnp feed.
RAFF:
FHD~I F~(so,~
8 7 . 8 m3h
2 . 5 0 N
HCI
SF:
F c ouF e C I , 36.22 g/L F a u FeClt

6.04 g/L
87,
4.38N
HCI
0 . 0 m3hb k d 6.00 N HCl
i
3 9 . 8 m3/h 6.00 N HCI
HYDROLYSIS
Figure C.2: Mass-balance conditions giving closed acid loop with 4.38 N HCI strip feed.
3.00
RCl
0.0 m ' h bleui 6 . 0 N HCI
47.9 mJm
6.00
N HCI
HYOROLYSIS
Figure (2.3: Mass-balance conditions giving closed acid loop with 4.88 N HCI strip feed.
st:
37.33 g/L F c o u F m '
SF:
233fi
13-95
538N
Fc(m)uFd3 F~TZ) u~ 0 ~ HCI
1 87.8 ~m3h
1 '
REDUCiON
1 3 . 9 5 gh F ~ U F C C I ~ 3.50N HCI
Figure C.4: Mass-balance conditions giving closed acid loop with 5.38 N HCl strip feed.
HAL OIF:
153.7 m ' h
25 gh F e 0 as F G ~ ( S Q ~
sofi
zo@)==Q
90lw fi
5& F m
m~zaso,
LO:
u g / L Fc(IIr)
SF:
0.44
263
& u & F a uF a t
HCI
87.81 m3n.
4.00 N
HCI
5.88N
Figure CS: Mass-balance conditions giving closed acid loop with 5.88 N HCl strip feed.
6.7 m'h Mctd
5.WN
HCl
6.00
N Ha
HYDROLrSIS
Figure C.6: Mass-balance conditions giving closed acid loop with 5.93 N HCI strip feed.
C . 2 CONCEPTUAL ELECTRO-ASSISTED STRIPPING ELECTROCHEMICAL

DATA
From the literature, data and materials relevant or applicable to electro-assisted stripping design were identified. No references involving electrolytic reduction of i r o n o to iron(II) at the cathode, while producing HCI at the anode, were found in the literature. As an alternative. selected findings for each of the two individual half-ce11 reactions of interest were taken fkom Liao (1997) and combined for the purposes of this discussion.
Infmation perinent to the cathode compcvfment
The major cathode information source was HCI electrolysis research where femc reduction
to ferrous was substituted for hydrogen evolution at the cathode. A platinum-coated titanium substrate cathode (Pt-Ti) and dimensionally stable anode @SA) were employed as electrodes. The HCl concentration was found to improve electrolyte condudvity and levels
as high as 4.8 N HCI caused no problems to the system. A temperature of 50C was found to
be more effective than 20C since the increased temperature increased solution conductivity,
consequently decreasing the operating ce11 voltage. As the current density was increased, the cathodic potential became more negative and the ohmic drop across the electrolyte increased. Sparging nitrogen in the catholyte narrowed the electrode diffision layer improving mass
transfer, thereby reducing the cathodic overpotential. A slight increase in ohmic drop was
observed due to the presence of the bubbles. A smaller cathodic overpotentiai allowed for non-hydrogen producing electrolysis to occur while operating at high current densities. Following this reasoning, a maximized catholyte flowrate would result in higher current densities which would fiirther reduce the required operating volumes and associated capital
costs.
The Pt-Ti electrode is a good choice for the highly corrosive strong HCl electrolytes. A
sacrifice in current density and gain in capital cost savings would undoubtedly result when
going fiom Pt-Ti to graphite as cathode material. The question of economic viability would
have to be addressed.
Infor&*on
pertinent to the MO&
comp4lfitient
The best anode reaaion would involve the clean regeneration of HCl via hydrogen oxidation.
Due to the poor aqueous solubility of H2 and the fact that current density is dependent upon
the Hz concentration at the electrode surface, a hydrogen diffision anode (HDA) would
prove necessary. Othewise, expected current densities could yield as low as 10 M'. Using
the HDA in NiC12-1-3 N HCI electrolytes operaieci at 50C (with Pt-Ti as cathode): (i) the
limitin~cument densiy improved from 250 h2 to 900 A I ? ; (ii) the anodic potential
Y
increased from -0.110 V to 0.1 10 V; and (iii) the ohrnic &op across the eiectrolyte increased
fiom 0.10 V to 0.25 V. The current efficiency at the anode was implied to be 100%. A rnaximized current density would be best to offset the high capital costs attributed to the use
of HDA electrodes. Conceming alternative electrode materials, graphite does not qualify as
an anode here since it catalyzes Cl2 formation which consumes it.

Wmated operathg cell voltage
With respect t o the anode cornpartment, the hydrogen diffision anode (HDA) approach is
clearly more advantageous than the SOo approach, avoiding the almost certain complexities
involved with the necessary containment, by the use of membranes, of the produced sulphate in the latter case. By using potential data fiom Liao (1997), the applied extemal ce11 voltage, while operating at 900 ~ to be 0.21 V ( - ( G - ~ J + & ~= -(0.30-0.11)+0.40 = mis estimated ~ , 0.21 V). Datais shown in Table C.1. Table C. 1: Estimation of electrode operating potentials (data fiorn Liao 1997). Cornpartment
wect(V)
Ch,
(A&) 900
Vdpd0.40 0.25
Ch,
(%)
HC1
3.8
1-3
FeCl3
+.30* Cathode (Pt-Ti) +0.110 Anode (KDA) *- NYg)sparging applied
900
92 100
C.3 PPELIMINAKY O P E R A ~ G COST-ANALYSIS
Table C.2 shows the results of a preliminary operating cost analysis. The total estimated operating cost per pound of nnc metal is listed for the electro-assisted stripping approaches,
with either H2(g)or SOW as reductant, versus conventional jarosite production. Electro-
reduction is expeaed to operate a t a low applied ceIl voltage (0.21 V) with either H2or S02,
which makes estimated power and reagent costs manageable. Sulfr dioxide demand is
assumed to be supplied by the on-site acid plant. Alsq only the benefits, not the cost of
nitrogen sparging, which optimizes cathodic potential, were considered at this point. Preliminary assessrnent indicates that zinc plant implementation with FeSX-Electro-stripping
is possible. As known universally, viability will be especially dependent upon the hematite
product selling price. Case C, which represents a goodquality iron oxide demanding a good
price from the iron-making industry, gives an overall debit of -1.8 centdbs Zn for both
electro-assisted stripping using Hu and the conventional jarosite route. Producing a higher purity iron product for magnetic or pigment applications that would sel1 at a higher price, would improve the economic viability. Hematite pnce estimates were acquired from Canadian and Amencan iron oxide operators/suppliers (Bialko 1998, Pape 1998, Poy 1998). Information pertaining to jarosite production was supplied by Houlachi (1998). Pyrohydrolysis costs were based on spray roasting information as fluid-bed figures, which are expected to be higher, were lirnited. Without considering more extensive operating costs
a
-
and assessrnent of market potential, expending the substantial amount in the associated capital costs cannot be justified at this point.
Table C.2: Preliminary O erating balance sheet (price estirnates fiom Bialko 1998, Houlachi 199 '!t ,Pape 1998, Foy 1998).
%CAN/lbs Za metal Solvent loss (100 pprn loss to both d n a t e s and stxip liquor) Acid plant sulfur dioxide gas (suppliai by acid plant) Hydrogen gas Electricai power Dohydrolysis (based on spray roasting cost estimate) Hematite sale at $0.0095/lbs et iron-ore pnce (worst case) Hematite sale at SO.0411bshematite for iron-making Hematite sale at $0.085/lbs hematite for iron-making Hematite sale at S0.14Abs hematite for magnetic and pigment Conventional Fe jaroste precipitation-jarofix treatrnent Conceptual hydrogen anode elechoreduction-pyrohydrolysis
Case A Case B Case C Case D
Debit Credit 0.003 173 O 0.003222 0.000 172 0.027495 - 0.001833 0.007699 0.016497 0.027495
[Conceptual SO anode electroreduction-pyrohydrolysis
0.018144 Case A 0.032229 Case B 0.026363 Case C 0.017565 Case D 0.006567 Case C 10.014343 1

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SEPARATION OF IRON(II1) FROM ZINC SULPHATESULPHURIC ACID SOLUTIONS USING

ORGANOPHOSPHORIC ACID EXTRACTANTS

Department of Mining and Metaiiurgical Engineering McGI University, Montreai

A Thesis submitted to the

Faculty of Graduate Stiidies and Research

@Frank T. Principe, 1999

National Library of Canada Acquisitions and Bibliographie Services

Bibliothque nationale du Canada

Acquisitions et services bibliographiques

To dear Dawn and our

fi)with the 'moderate strength'

L'extraction par solvant du

de solutions de procd d'extraction de zinc via

H2S04 forte concentration, et la prparation de solutions de r-extraction concentres de

de rextraction (source). Le 1.25 F D2EHPA comporte certains avantages relativement au

slectivit ~ e ~ + / et ~ une n ~capacit + d'absorption de

fera comparable (-20 f i )lorsque

1.1 INDUSTRIAL ZINC PRODUCTION .......................................................... 1

under shrdy ................................................................... 6

1.3.2 Main objective .............................................................................. 6

2 LITERATURE REViEW AND THEORY

1.3.3 mesis outhe ................................................................................ 6

4 0 ICESULTS AND DISCUSSION

4.1 EXTRACTANT SOLUBILITY AND STABILI'IY

4.2.3 IronflII)Z d n g chmacterislics ......................................................... 63

.............................................................. 76 4.3.3 EffectufFeCIz onst~pping

5. CONCLUSIONS AND RlECOMMENDATIONS

5.1 CONCLUSIONS ................................................................................. 96 5.2 RECOMMENDATIONS FOR FUTURE WORK ........................................... 98

APPENDIX A MODIFIED FREE ACID TITRATION METHODOLOGY

A 1 Free acid determination in strong H2SOcF~(SO4h-ZnSOqa ........................ 105

114 116 119

C.2 Concephial electro-assistecl stripping electrochemical data ............................. 129

C.3 Preliminary operating cost analysis ......................................................... 130

Figure 32:Schematic of experimental apparatus for solubility. extraction, and

Table 4.5. Extractant solubility-degradationin aqueous and strip feeds (A/*

Table 4.6. Zinc loading ( A / M . O . pIS04]o= 50 g/L)............................................57

........................... 1 13 Table B. 1: Equilibria in the aqueous system F~~'-OH.-SO~--PO~*.

Table B.4:Calculated stability constants. ......................................................... 117

1.1.1 Rout-leach-electrowin process (RLE)

h e conventionai RLE flowsheet is given in Figure 1.1. The solubilized Z n 0 calcine. T

final zinc product

Zn Calcine (60% Zn, 10% Fe)

i NL: neutral leach

j PUR: purification 1 [ EW: electrowinning i :HAL: hot acidleach i

Figure 1.1: Conventional zinc roast-leach-electrowin process flowsheet.

Hydrotytic precipitation of iron as a means of iron rejection is presently being employed in

by 18 plants while goethitelparagoethite and hematite are produced at 6 and 1 plant(s),

catastrophic effcts to downstream electfowinning, i.e. loss of m e n t efnciency.

Minimal S camy-over to the strip liquor to ensure uon by-product purity.

Minimal organic losses to aqueous streams to controi solvent costs.

Z n Calcine (60% Zn,10% Fe)

4AQUEOUS FEED PHASE

Figure 1.3: Iron solvent extraction stages in the concephial flowsheet.

1.3.1 Extractants under study

The extractants, octylphenyl acid phosphate (OPAP) and di-(2-ethylhexyl)phosphoric acid

context of an integrated FeSX-Zn RLE flowsheet.

2. Literature Review and Theory

exttactants: Versatic acid

hydroxamic acid (NED) (Lakshmanan et al. 1996); and an aminomethylene-phosphonic acid

D2EHPA and OPAF!

Despite the large body of literature available on DZEHPA, there is a

Kamagarni 1988, Green and Harbuck 1995).