Aqueous Processing Overview

Aqueous Lixiviants: Principle, Types,

and Applications
Shijie Wang

Aqueous lixiviant is a leach liquour vative developments of aqueous lixivi- from anodic to cathodic electrode surface
capable of dissolving all or part of ore ants in the metallurgical leaching pro- sites, may be represented by Equation
or concentrate. It plays a critical role in cesses. 1. (All equations are shown in the Equa-
the hydrometallurgical process. Although tions table on page 38.)
PRINCIPLE OF AQUEOUS
cyanide leaching of gold and silver has For n x 0, A represents the reactant in
LIXIVIATION
demonstrated success in the industry for the oxidized state, while B is in the
100 years, searching for innovative In aqueous lixiviation, the liquid state reduced state. According to the Nernst
lixiviants to leach gold, copper, and other and the inter-ionic attractions may be Equation 2, where E and E0 are the half-
heavy metals effectively, economically, mentioned, but special attention is cell and standard half-cell potentials for
and environmentally has never stopped. focused on the directly observable mac- the reaction, which are related to free
This paper reviews the aqueous lixivi- roscopic properties of leaching solutions. energy by $G = –nFE and $G0 = –nFE0,
ant’s principle, summarizes the types This emphasis on the most engaging n is the number of electrons transferred
used in numerous sites, and presents its features of the principle of aqueous in the reaction and F is the Faraday
new applications. lixiviation involves thermodynamics and number (23,060 cal/mol). At room tem-
kinetics of chemical reactions, which are perature and when the activity of water,
INTRODUCTION
important and thoroughly involved in A H O, is taken as unity, the reaction
2
People who are tea lovers know that, metallurgical leach processes. becomes Equation 3.
after selecting high-quality tea, the most The equation shows that, when an
Thermodynamic Aspects
important component in making tea is electron transfer is involved, the reaction
the water. To make delicious tea, the Equilibrium reactions in the solid- completion is determined by E and
water has to be boiling such that the aqueous solution interface may be solution pH. The classification of this
oxygen still dissolved in it can release characterized in two ways: those where chemical reaction, all types of oxida-
the full flavor of the tea. Indeed, making oxidation does occur and those where it tion/reduction, non-oxy/red reactions,
great tea is a leaching process, and the does not. If oxidation-reduction couples and their related decisive equilibria in
fresh boiling water is a perfect aqueous exist in the reaction, electrons must be the solution are given in Table I.
lixiviant that extracts soluble constitu- transferred. An electrochemical reaction, As shown in Table I, each chemical
ents, such as the taste, enzymes, and in which electrons flow through the solid reaction in the solution relates to com-
therapeutic properties, from tea.
In extractive metallurgy, leaching is Table I. Classification of Chemical Reactions in the Solution
known as an extraction widely used in
Types Chemical Reactions Equilibrium
metal recovery since many metals can
form soluble salts in aqueous media. The Oxidation/Reduction
aqueous lixiviant that can be included H+  0, e–  0 aA + mH+ + ne– = bB + cH2O pH, E (m  0, n  0)
in the scope of metallurgical leaching 0.059
E = E0 + (blgAB–mpH – algAA)
includes not only water, but also acids, n
bases, and aqueous salt solutions. It is
crucial to choose a lixiviant that meets H+ = 0, e–  0 aA + ne– = bB E (m = 0, n  0)
all needs of leaching the desired con- 0
0.059
E =E + (blgAB – algAA)
stituent selectively and efficiently. n
Leaching has been referred to as a Non-oxidation/Reduction
relatively recent technology for metals H+  0, e– = 0 aA + mH+ = bB + cH2O pH (m  0, n = 0)
recovery, and aqueous lixiviant needs to 1
be recognized for its important role in pH = pH0 – (blgAB –algAA)
m
leaching processes. This paper is H+ = 0, e– = 0 aA = bB K (m = 0, n = 0)
designed to give an overview of the lgK = blgAB – algAA
principles, types, applications, and inno-

2007 October • JOM 37

position activity, half-cell potential, and solid, gaseous, and dissolved compo- necessary for natural occurrence of the
pH value. For a given temperature and nents in equilibrium. In this uranium- reaction, indicating stability relation-
pressure, these activities, potentials, and carbonate-H2O system,2 it is suggested ships and the formation sequence of
pH can be presented in a potential-pH that the first step in the extraction of surface reaction layers, and providing
diagram (or Pourbaix diagram1), where uranium is the oxidation of tetravalent basic guidance in choosing the combina-
thermodynamic equilibrium data are uranium to its hexavalent state and the tion of reagents and their concentrations
graphically shown and species presented second step is the formation of uranium so as to obtain favorable free energy
at certain conditions are indicated. The carbonate-complex species that are changes associated with proposed reac-
general conditions likely to favor dis- soluble. tions.
solution may also be derived from the Developed originally for corrosion
Kinetics Aspects
thermodynamic data presented in the studies, Pourbaix diagrams have gained
form of Pourbaix diagrams. As an widespread acceptance in hydrometal- Assume a spherical particle in which
example shown in Figure 1, the Pourbaix lurgy. They are important in metallurgi- the moving reaction zone is essentially
diagram is a plot of Eh versus pH for cal leaching for predicting the conditions constant and independent of the mineral
particle-size distribution illustrated in
Equations Figure 2 for the type of core leaching in
the presence of excess aqueous
aA + mH+ + ne– = bB + cH2O (1) 4Cu(NH3)42+ + Au + 3S2O32– lixiviant(s). The rate of reaction within
m Au(NH3)2+ + Cu(S2O3)35– + 2NH3 (16) the reaction zone may be expressed by
RT « [B]b [H2 O]e º Equation 4,3 where N is moles of leach-
E  E0  ln ¬ » (2)
nF ­ [A ]a [H ]m ¼ Au(NH3)2+ + 2S2O32– able minerals, N = 4/3Pr3Rs/Ms, (Rs and
m Au(S2O3)23– + 2NH3 (17) Ms are solid molecular weight and den-
0.059
E = E0 + (blgAB – mpH – algAA) (3) sity), A is average area per particle in
n
the reaction zone, A = 4 ʌr2, Ks is a
dN 4Au + 8SO32–+ O2 + 2H2O
rate = – = KsAC (4) specific rate constant of the mineral
dt m 4Au(S2O3)23– + 4OH– (18)
particle, and C is bulk concentration
(mole) in the reaction zone.
dN 4Pr 2Rs dr (5) Anode: CuFeS2 m Cu2+ + Fe2+ + 2S0 + 4e– (19)
 Equation 5 may be integrated for
dt Ms dt
steady-state transport and combined with
r
Ms
t Cathode: 4Fe3+ + 4e– m 4Fe2+ (20) a fraction reacted, A, for a matrix-block
° dr  K s C
Rs °0
dt (6) fragment of radius r. Combining this
0
CuFeS2(s) + 2Fe2(SO4)3 (a) with Equation 4, –4Pr2Rs/Msdr/dt =
R m CuSO4 (a) + 5 FeSO4 (a) + 2S0(s) (21) 4Pr2KsC, gives Equations 6 and 7.
r0 r  K s C s t (7) N
Ms Assuming Ni = initial moles, Ni –
Ni
Pb + 2Fe(BF4)3 m 2Fe(BF4)2 + Pb(BF4)2 (22) r3
¥ M ´ = A = r03 – 3 , or, r = r0 (1 – A)1/3 , then,
1 (1 A)1/ 3  ¦ K s C s µ t  K exp t (8) r0
§ Rsr0 ¶
2Fe(BF4)2 + 2HBF4 + H2O2 the rate of the reaction is shown in Equa-
m 2Fe(BF4)3 + H2O (23) tion 8.
dC dC
rate  AD  Pr 2D (9) For a reaction zone with thickness
dr dr
Cu + 2Fe(BF4)3 m 2Fe(BF4)2 + Cu(BF4)2 (24) moving inward chemically during the
r0
c
R dr course of the reaction, illustrated in
° dC  4PD °r r
c
2
(10)
As + 3Fe(BF4)3 m 3Fe(BF4)2 + As (BF4)3 (25)
Figure 3, the rate of reaction within the
s
reaction zone may be expressed by Equa-
R ¥ 1 1´ tion 9, where A is average area per
C CS  (11)
4PD ¦§ r1 r0 µ¶ Bi + 3Fe(BF4)3 m 3Fe(BF4)2 + Bi(BF4)3 (26) particle in the reaction zone and D is
diffusion through pores to the reaction
dN R dr zone (see Equations 10 and 11), where
 4Pr13 s 1 (12) Sb + 3Fe(BF4)3 m 3Fe(BF4)2 + Sb(BF4)3 (27)
dt Ms dt 4PDC
Cs = 0 and R = .
r t Sb2S3 + 6Fe(BF4)3 [(r0 r) / r0 r]
¥ r2 ´ M
° ¦ r1 1 µ dr1  DC s a ° dt (13) m 2Sb(BF4)3 + 6Fe(BF4)2 + 3S0 (28)
r §
r0 ¶ Rs 0 When moles in the core =
4 R
2
2 2M DCat Cu2S + 4Fe(BF4)3 N  P r13 s , then Equation 12
(1 A) 3 1  A s  K exp t (14) m 2Cu(BF4)2 + 4Fe(BF4)2 + S0 (29)
3 Ms
3 r02Rs
results.
5–
4Cu(S2O ) + O2 + 16NH3 + 2H2O Mo2S + 4Fe(BF4)3 The rate of diffusion is equated with
3 3
m 4Cu(NH3)42+ + 12S2O32– + 4OH– (15) m 2Mo(BF4)2 + 6Fe(BF4)2 + S0 (30) dN
the rate of reaction of the core, =
dt

38 JOM • October 2007

aR, where a = (moles of core reacted)/ These include acids, bases, and salts.
(moles of reactant transferred through There are several qualifications an aque-
layer). These values are then rearranged ous lixiviant should satisfy, with reagent
as Equation 13. cost being one of the more important.
Again, in terms of fraction reacted, Other qualifications are the ability to
selectively dissolve the desired metal,
4 3 4
Pr0 Rs Pr13Rs r 3 r 3 the ease of procuring and handling, the
A 3 3  03 13 ; then, ability to be regenerated and reused, and
4 3 r0 r0
Pr R the extent to which it corrodes process
3 0 s equipment. The classification of chemi-
the rate of the reaction based on a reac- cal reagents for aqueous lixiviants com-
tion-controlled process is Equation 14. monly used in metallurgical leaching is
As shown in Equations 8 and 14, the summarized in Table II.
nature of the proceeding reactions and Figure 2. An Illustrated reaction zone
Acids
the speed in lixiviation can be greatly (assume sphere).
influenced by the bulk concentrations Sulfuric acid (H2SO4), once known
of aqueous lixiviants. Since the reagent as oil of vitriol, is a strong mineral acid
concentration at the particle surface is that is soluble in water at all concentra- leaching wolframite and scheelite ores.4
lower, the leaching rate greatly depends tions. It is probably the most widely Ammonium hydroxide (NH4OH), whose
on the initial concentration of the lixivi- used lixiviant with its aggressiveness, aqueous solutions are sometimes referred
ant. The higher the initial concentration, price, and general availability balancing to as ammonia water or aqua ammonia,
the faster the leaching rate will be. The its nonselectivity. Sulfuric acid is used can dissolve various metal oxides and
leaching rate slows as the consumption either dilute, concentrated (600 Bé or hydroxides such as copper(II) hydroxide
of lixiviant increases. Normally, higher 93%), or combined with oxygen. to form ammine complexes. In this case,
concentrations of the lixiviant are needed Nitric acid (HNO3), also known as the active reagent is the ammonia, not
to produce comparable leach kinetics. In aqua fortis, is an aqueous solution of the hydroxide salt.
practice, the usage of leaching lixiviant hydrogen nitrate. Being a powerful oxi-
Aqueous Salt Solution
will be calculated by agent consumption, dizing reagent, nitric acid reacts violently
residual concentration, and the percent of with many metallic compounds in the Salts are often referred to only by the
solids in the leaching, etc., and is often leaching. name of the cation (e.g., sodium salt,
kept 1.5 to 2 times the stoichiometric Hydrochloric acid (HCl), which was ammonium salt, and ferric salt), or by
ratio of the chemical reaction. once known as muriatic acid, is the the name of the anion, (e.g., cyanide and
aqueous solution of hydrogen chloride chloride). Ammonium salt has long been
TYPES OF AQUEOUS
gas that is a fine solvent widely used in known by the term Hammoniacus sal’s,
LIXIVIANTS
leaching because of its nonselectivity and appearing in the writings of Pliny. One
Many lixiviants are known that will heavy attack on leaching metal/minerals. great characteristic property of ammo-
form aqueous solutions capable of dis- When dissolved in water, chlorine forms nia is its power of combining directly
solving metals from ores or concentrates. hydrochloric acid and hypochlorous with acids to form salts; hence, with
acid which then gradually decomposes hydrochloric acid it forms ammonium
into hydrochloric acid and oxygen. This chloride (sal-ammoniac); with nitric
powerful oxidizing action is utilized for acid, ammonium nitrate, etc. The salts
leaching sulfide ores and gold-bearing produced by the action of ammonia on
materials. acids are known as ammonium salts and
Aqua Regia (HNO3 + HCl), Latin all contain the ammonium ion (NH4+).
for king’s water, is a highly corrosive, Cyanide salt is a salt that contains the
fuming yellow or red solution. It is made “cyano group,” CyN, which consists of a
by mixing freshly concentrated nitric and carbon atom triple-bonded to a nitrogen
hydrochloric acids in a volumetric ratio atom. Cyanide is the anion CN–. Sodium
of one to three, respectively. It is one of salts generally include sodium chloride,
the few reagents that can dissolve gold sodium sulfide, sodium cyanide, and
and platinum. sodium thiosulfate, which have been
widely used in various metallurgical
Bases
leaching processes.5
Sodium hydroxide (NaOH), also
Effective Oxidants
known as caustic or lye, forms a strong
alkaline solution when dissolved in a The leaching of naturally occurring
Figure 1. An Eh-pH diagram for uranium- solvent such as water. It is used chiefly minerals often requires oxidation. The
carbonate-H2O system. for dissolving aluminum from bauxite, lixiviants to be considered effective
for opening monazite sand, and for oxidants in leaching are Fe(II)/Fe(III),

2007 October • JOM 39

 copper concentrates but is particularly
Table II. Types of Leaching and the Aqueous Lixiviants in Common Use
suitable for those predominantly consist-
Types of Leaching Reagents for Aqueous Lixiviants ing of the monovalent minerals chalcoc-
Acid H2SO4, HNO3, HCl, Aqua Regia, ite and bornite, as only dissolution of the
Alkaline NaOH, NH4OH readily soluble copper is attempted.8 The
Salt NaCN, NaCl, Na2S, FeCl3, CuCl2, Fe2(SO4)3, Na2S2O3 ammonia leach process produces 5–9’s
Pressure Acid or alkaline pure copper through its leach-solvent
Bacteria Fe2(SO4)3 + bacteria (i.e., T. ferrooxidans) + H2SO4 extraction-electrowinning (SX-EW) cir-
Water H2O cuits because ammonia leach eliminates
many of the impurities typically carried
over to the electrowinning circuit when
oxygen, and hydrogen peroxide. Many sulfuric acid leaching is used.
Application in Gold Leaching
important oxidation and reduction The pilot plant tests9 have concluded
reactions, using effective oxidants or Chlorine was the first commercial gold that the Cu+ disproportionates to form
involving complex ions or oxy-anions, extracting agent, introduced on the Cu0 and CuS; that only the Cu0 oxidizes
are presented here. These reactions are market as “DuPont mining salts” in the and dissolves; and that CuS requires a
not all-inclusive but simply represent late 1800s. The method agitated ore and much longer time and/or more intensive
important reactants currently used in chlorine in a “Pachuca Tank” (rotating oxidizing conditions to dissolve. In the
leaching. the mixture in lead-lined barrels) and operation, however, the CuS is concen-
v Reactions involving molecular fell into disfavor with the discovery that trated by residue flotation and sent to the
oxidants and reductants: 2Fe+2 + cyanide extraction was superior due to smelter. The advantage of the process
O2 + H+ m 2Fe+3 + H2O2 and 2Fe+2 its simplicity, availability of chemicals, is that it quickly recovers about 50% of
+ H2O2 + 2H+ ĺ 2Fe+3 + H2O.. and low cost. the copper in concentrate, which brings
v Reactions between metal ions: Currently, diluted alkaline cyanide a swift cash return to the mine.
Fe+2 + Ce+4 m Fe+3 + Ce+3, solutions are used exclusively with dis-
Application in Solution Mining
activation energy: repulsive force solved oxygen for gold dissolution in
between Fe+2 and Ce+4 at two gold mines because the gold cyanide Solution mining, or in-situ mining,
angstrom separation. complex (Au(CN)2–) yields higher gold is designed to co-exist with other land
v Reactions involving oxy-anions recovery, achieved by loading onto uses such as agriculture. The in-situ
such as MnO2–, Cr2O72–: 2MnO2– + carbon in the well-established carbon- mine will typically consist of a series
3H2 + 2H+ m 2MnO2 + 4H2O and in-pulp and carbon-in-leach processes. of injection wells and recovery wells. At
ClO3– + SO3– m ClO2– + 5O4–2. Four cyanide salts, potassium, sodium, the level where the drill hold penetrates
v Reactions involving complex ions: ammonia, and calcium, have been tested the copper-bearing rock, perforations
Co(NH3)5Cl+2 + Cr+2 m [(NH3)5Co or commercially used in aqueous lix- in the casing allow a weak sulfuric acid
– Cl – Cr]+4 m Co(NH3)5+2 + iviation. Their order of increasing abili- enriched with air sparging or ferric to
CrCl+2, where Cl– gives e– to Co+3, ties in the dissolution of gold is: NH4CN be injected through fractures, pores, or
Cr+2 gives e– to Cl–). Redox > Ca(CN)2 > NaCN > KCN. The order diffuses to dissolve the metal from ores.
reactions catalyze by OH–, Cl–, F–, of increasing stabilities in air containing The metal-bearing leach solution is then
oxidation/reduction occur by atom carbon dioxide is: KCN > NaCN > drawn up through the recovery wells for
transfer in some cases. NH4CN > Ca(CN)2. KCN was used in processing at a surface plant.
dissolving gold in the early days of Solution mining was first used as
APPLICATIONS OF
cyanidation, but NaCN is widely a means to extract low grades of ura-
AQUEOUS LIXIVIANTS
employed today because of its dissolu- nium from ore in underground mines.
Metallurgical leaching carries out the tion ability, stability, and cost. The aqueous lixiviant in the leaching
task of dissolving the value mineral of is the “miner” where the leach solu-
Application in Copper Ammonia
concentrate/ore in an aqueous lixiviant tion changes along its path. Either the
Leaching
solution. Applications of aqueous lix- ammonium carbonate [(NH4)2CO3] or
iviants in acid and salt leaching of heavy The first ammonia leaching was sodium bicarbonate (NaHCO3) enriched
metals and precious metals from con- applied to copper carbonate and native with hydrogen peroxide (H2O2) is used
centrates and slimes have been copper tailings in 1915. The first com- for alkaline leaching. The weak sulfuric
described.6,7 More specific applications mercial ammonia leaching of sulfide acid enriched with air sparging or ferric
of aqueous lixiviants in the leaching of concentrates with oxygen was estab- is used for acid leaching.10
individual minerals are listed in Table lished in 1974. BHP’s Coloso plant used An in-situ mining method using a
III. Traditional and typical applications, a similar flowsheet but with air and low dilute sulfuric acid leach solution for
which may have revolutionary implica- temperatures to avoid sulfate production a deep copper-oxide deposit near Casa
tions for cost-effective and environmen- and commissioned ammonia leaching Grande, Arizona, was developed by the
tally compatible processes in the hydro- production, leaching part of Escondida’s former U.S. Bureau of Mines11 in 1986.
metallurgical industry, are described in concentrates in late 1994. Laboratory experiments and in-situ leach
the following. The process is applicable to many tests conducted focused on the leach-

40 JOM • October 2007

 guarantee the continued dissolution of
chalcopyrite in the leaching, the ferric
sulfate leaching, or Galvanox process,
is developed with the galvanic effect
between chalcopyrite and pyrite.15 This
leaching makes use of the concept that
Figure 3. A mineral chalcopyrite is a semiconductor and
fragment illustrat- corrodes electrochemically in oxidiz-
ing reacted and
unreacted regions ing solutions; the reaction may be
(assume pore layer represented as a combination of anodic
diffusion). and cathodic half-cells, as presented in
Equations 19 and 20. The overall reaction
is given in Equation 21.
ing characteristics of various ore types copper-ammonia-thiosulfate process are Using the aqueous lixiviant of ferric
as well as the influence of mineralogy, found to be suitable for ores from a few sulfate with galvanic assistance in atmo-
mineral chemistry, and rock texture on other mining companies, but they are spheric leaching, the adequate lixiviant
these leaching characteristics. This could not universally applicable.14 of ferric sulfate’s contact with the chal-
lead to innovative and low-cost copper copyrite particle surface is guaranteed
Galvanically Assisted Ferric
mining methods. and copper recovery of 98+% is claimed
Sulfate Leaching
to be achieved at 80˚C in 4 hours.
INNOVATIVE
During chalcopyrite (CuFeS2) leach-
DEVELOPMENTS OF Ferric Fluoborate Leaching:
ing, a passivating film that most likely
AQUEOUS LIXIVIANTS An Innovative Lixiviant
consists of an altered, partially iron-
The successful and universal appli- depleted sulfide layer forms. It becomes The Fluobor process was originally
cation of gold cyanide leaching is an resistant to electrochemical breakdown developed as an aqueous process for
excellent illustration that critical aque- in ferric sulfate solution and results in recovering lead from lead-acid battery
ous lixiviants play important roles in chalcopyrite surface passivation. To metal scrap and directly from galena.16
the leaching of concentrates/ores. In
fact, people have never stopped trying Table III. Lixiviants Applied to Leaching of Ores
to innovate aqueous lixiviants for metal
recoveries, and have extensively tested Aqueous Lixiviant Minerals Chemical Formula
new findings in recent times. This has Dilute Sulfuric Acid Uranniobite UO2
been paralleled with the revival pressure Tenorite CuO
and bacterial leaching developments in
Cacoxenite Fe4(PO4)3(OH)3·12H2O
mining industries.
Pyrrhotite Fe1-xS
Thiosulfate Leaching: Gold Dilute Sulfuric Acid + Oxidants Cuprite Cu2O
Leach Alternatives Chalcuprite CuFeS2
Lixiviants such as thiourea, thiosul- Uranniobite UO2
phate, bromide, and iodide solutions Pitchblende (U,Th)O2
have been studied12 and concluded to be Hydrochloric Acid Bismuthinite Bi2S3
potential alternatives to cyanide leaching. Apatite Ca5[PO4]3(F,Cl,OH)
A process based on thiosulfate leaching Tenstite CaWO4
followed by resin-in-pulp gold extraction Cerium Oxalate Ce2(C2O4)3·10H2O
was developed to treat the carbonaceous, Antimonite Sb2S3
preg-robbing ores.13 These ores have Cerusite PbCO3
proven to be amenable to thiosulfate
Hot Concentrated Sulfuric Acid Monazite (Ce,La,Y,Th)[PO4]
leaching under mild conditions where
Pyrochloride (Ca,Ce)2Nb2(O,F)7
thiosulfate, ammonium, copper ions,
Uranotantalite (Y,U,Fe,Th)(Nb,Ta)2O6
and oxygen are involved, as shown in
Equations 15–18. Ytterbite Be2FeY2SiO10
The explanation for a possible mecha- Nitric Acid Molybdenite MoS2
nistic scheme is that the copper ions act as Tantapyrochlore (Na,Ca)2Ta2O6(O,OH,F)
an oxidation catalyst and that ammonium Tapaltite Ag3Bi(S,Te)3
ions are important to maintain copper in Argenite Ag2S
solution at the alkaline pH. In the treat- Argyrythrose Ag3SbS3
ment of preg-robbing ores, thiosulfate Sodium Hydroxide Monhydrallite Al2O3·H2O
leaching yields higher gold recovery than Monazite (Ce,La,Y,Th)[PO4]
cyanide does. The same conditions of the

2007 October • JOM 41

The ferric fluoborate was then innova- proven leaching solution, such as cyanide (the Paul E. Queneau International Symposium),
tively developed for pilot leaching of lead solution, which has been universally Volume I: Fundamental Aspects, ed. R.G. Reddy et al.
(Warrendale, PA: TMS, 1993), pp. 949–969.
bullion and its insoluble sludge.17,18 The employed in gold leaching for over 100 9. N. Arbiter and T. McNulty, “Ammonia Leaching of
overall chemical reactions are given in years, the continuous improvement of Copper Sulfide Concentrates,” Copper 99 Vol. IV
Equations 22–27. existing common aqueous lixiviants for – Hydrometallurgy, ed. S.K. Young et al. (Warrendale,
PA: TMS 1999), pp. 197–212.
As shown in Equation 23, ferrous detailed characterization of a deposit 10. S. Orr and A. Gehahun, “Hydro-Geo-Chemistry
ions are oxidized to ferric by hydrogen should be never stopped. Further, the and Management of In-Situ Uranium Leaching”
peroxide in a fluoboric acid solution. innovative developments of new aqueous (Presentation given at 2007 SME Annual Meeting,
Denver, Colorado, February 25–28, 2007).
Equations 23 through 27 are also oxi- lixiviants for aggressiveness, cheapness, 11. D.J. Millenacker, “In-Situ Mining,” E&MJ (September
dation reactions that consume ferric and fit in the recovery process should 1989), pp. 56–58.
to solubilize the copper, arsenic, bis- always be awarded. 12.R.Y.Wan,J.D.Miller,andJ.Li,“Thiohydrometallurgical
Processes for Gold Recovery, Innovations in Natural
muth, and antimony in the fluoborate An ideal aqueous lixiviant, with Resource Processing,” Proceedings of the Jan K.
system. The dissolution mechanism of emphasis on leachability and selectivity, Miller Symposium (Littleton, CO: Society for Mining,
the leaching is ferric oxidation rather should be capable of being designed with Metallurgy, and Exploration, Inc., 2005), pp. 223–244.
13. C.A. Fleming et al., “Recent Advances in the
than fluoboric acid dissolution, which an affinity to the selected metal ion, have Development of an Alternative to the Cyanidation
incorporates the concepts of using the a powerful oxidizer if necessary, and be Process: Thiosulfate Leaching and Resin in Pulp,”
ferrous/ferric couple as the oxidant and amenable to the chosen metal recovery Minerals & Metallurgical Processing, 20 (1) (2003),
pp. 1–9.
stabilizing the fluoborate anion at the processing. A day with new cost-effec- 14. J. McMullen, personal communication (9 July
leaching temperature. The silver and gold tive and environmentally sound aqueous 2007).
contents of sludge (or the leach residue) lixiviants will come. 15. D.G. Dixon, D.D. Mayne, and K.G. Baxter,
“GALVANOXTM —A Novel Process for Recovery of
were significantly concentrated after the Copper from Primary Copper Concentrates,” Copper
preferential dissolution of minor metals References 2007, the 6th International Conference, held in Toronto,
in a single leaching stage. ON, Canada, August 25–30, 2007.
1. M. Pourbaix, Atlas of Electrochemical Equilibria in 16. M. Olper and P.L. Fracchia, “Hydrometallurgical
The ferric fluoborate lixiviants were Solutions (New York: Pergamon Press, 1966). Process for an Overall Recovery of the Components of
also bench-scale tested in the leaching 2. R.G. Reddy, S.Wang, and A.E.Torma, “A Preliminary Exhausted Lead-Acid Batteries,” U.S. patent 4,769,116
Thermodynamic Study of Bacterial Attachment on (6 September 1988).
of tetrahedrite and molybdenum con- Uranium Contaminated Soils from Fernald,” Biohydro- 17. F. Ojebuoboh, S. Wang, and M. Maccagni,
centrates, respectively.19,20 The chemi- metallurgical Technologies, ed. A.E. Torma etc. “Refining Primary Lead by Granulation-Leaching-
cal reactions are shown in Equations (Warrendale, PA: TMS, 1993), pp. 715–729. Electrowinning,” JOM, 55 (4) (2003), pp. 19–23.
3. M.C. Fuerstenau, Hydrometallurgy notes (University 18. S. Wang, F. Ojebuoboh, and M.G. King, “The
28–30. of Nevada-Reno, December 1990). Fluoborate Treatment of Sludge from the Electrolytic
4. Fathi Habashi, Principles of Extractive Metallurgy, Refining of Granulated Lead,” JOM, 55 (4) (2003), pp.
CONCLUSION Vol. 2 (New York: Gordon and Breach, 1970). 24–27.
5. L.H. Huang, Chemical Mineral Processing (Beijing: 19. S. Wang, “Process Development for Recovery of
Aqueous lixiviants have and continue The Metallurgical Industrial Press, 1990) (in Chinese). Cu, Sb, and Ag from Tetrahedrite Concentrates,” SME
to play a critical role in leaching pro- 6. S. Wang, “Copper Leaching from Chalcopyrite Transactions, 312 (2002), pp. 101–103.
cesses. They not only present the vari- Concentrates,” JOM, 57 (7) (2005), pp. 49–51. 20. S. Wang, Laboratory Notes, Asarco Technical
7. J.E. Hoffmann et al., Copper 95 Vol. III, Services Center, Salt Lake City, UT (August 2001).
ous unique aspects of reagents used to Hydrometallurgical Processing of Kennecott Refinery
satisfy leaching needs, but also involve Slimes, ed. W.C. Copper etc. (Montreal, Canada: The
the “breaking” and making of interac- Metallurgical Society of CIM, 1995), pp. 41–57. ShijieWang is senior engineer of Copper Operations
8. W.P.C. Duyvesteyn and B.J. Sabacky, “The at Kennecott Utah Copper, 11500 West 2100 South,
tions between particles in solution. Escondida Process for Copper Concentrates,” P.O. Box 6001, Magna, UT 84044; (801) 569-6747; fax
Although it is a challenge to replace a Extractive Metallurgy of Copper, Nickel and Cobalt (801) 569-6753; e-mail [email protected].

42 JOM • October 2007