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Ligand selection for complex-leaching valuable metals in hydrometallurgy

YANG Tian-zu(), DOU Ai-chun(), LEI Cun-mao(), REN Jin( ), LIU Zhen-zhen()
School of Metallurgical Science and Engineering, Central South University, Changsha 410083, China
Received 6 July 2009; accepted 19 November 2009

Abstract: A two-stage ligand selection method composed of a primary selection and a critical selection, for complex-leaching
valuable metals was presented. At the primary selection stage, three conditions were discussed under a supposed ideal state by
mathematical derivation. Generally, ligands selected under conditionwere easier for complex-leaching valuable metals than that
under condition , however, under condition , ligands selected were hard to complex-leaching the valuable metals. Ligands that
were out of these three conditions could be disposed directly. In critical selection, ligands selected in primary selection can be
finalized. Case applications were provided for verifying the method. The application indicated that iminodiacetate (Ida2) can be used
as a complex agent for complex-leaching smithsonite (ZnCO3); the leaching condition should be controlled with pH 811; the
relative error of the minimum consumption of Ida2 between the predicted and the calculated results is 5.3%. The results indicate that
the theoretical derivations in the ideal state are reliable, and the method for ligand selection is practical and operable.
Key words: ligand selection; complex-leaching; smithsonite; hydrometallurgy

with valuable metal ions (Cu2+, Zn2+) in ammonia


1 Introduction leaching. In this process, ammonia evaporates, which
causes the environment pollution. Current studies[68]
Nowadays, with the depletion of copper, zinc still focus on utilizing ammonium to substitute part of
sulphuric ores are easily upgraded by floatation. ammonia to alleviate the environmental problem.
However, the low grade oxide ores are difficult to be Referring to caustic soda leaching[910], OH is used as
upgraded and smelt, which draws more and more a leaching ligand to coordinate with metal ions. The
attention and thus various hydrometallurgical methods ligand (OH) and the metal ion (Zn2+) are combined to
have been developed to leach these low grade oxiGe ores. form the 4th complex Zn(OH)42 with high concentrated
The processes include bioleaching, acid leaching, and caustic soda in the solution, which requires large
alkaline leaching. In bioleaching[12] bacteria are used consumption of leaching reagent. While increasing the
to leach ores. It is reported that the bacteria are difficult concentration of NaOH, SiO2 in the ore can be dissolved
to be domesticated for the low metals recovery and slow into the solution, which consumes more NaOH. The
reaction rate, which constrains the development of this reasons mentioned above constrain the process
process. Acid leaching[35] occurs in the acidic media. development. Moreover, because the improper ligands
As we all know, impurities such as Ca, Mg, Fe and Si used in the alkaline leaching process seriously affect the
can be dissolved in these media, which contaminate the mineral resources utilization, it is urgent to study new
leaching liquor and consume leaching reagent. Si is ligands (or leaching reagents) to treat these low grade
always formed as silica gels in the system and affects the oxide ores, which is of great strategic significance for
slurry filtration. This limits the process development. effective utilization and sustainable development of
Recently, more and more studies focus on the alkaline nonferrous metals.
leaching process in which valuable metals can be The primary purpose of complex-leaching is to
selectively separated with impurities by the formation of selectively separate valuable metals with impurities by
complexes. Alkaline leaching mainly contains ammonia generating complexes. And the main purpose is to
leaching and caustic soda leaching by using different dissolve the valuable metals Cu and Zn in leaching liquor
ligands. NH3 is used as a leaching ligand to coordinate and leave the impurities, such as Ca, Mg, Fe and Si in

Foundation item: Project(2007CB613604) supported by the National Basic Research Program of China
Corresponding author: YANG Tian-zu; Tel: +86-731-88836791; E-mail: tianzuyang@163.com
DOI: 10.1016/S1003-6326(09)60270-3
YANG Tian-zu, et al/Trans. Nonferrous Met. Soc. China 20(2010) 11481153 1149
residue. Because the valuable metals in the oxide ore are M+iL=MLi (i=1, 2, 3, , x) (4)
mainly in form of carbonates, basic carbonates are
[ML i ]
insoluble compounds. The recovery of valuable metals E Li
[M][L]i
by complex-leaching can be achieved by dissolving these
insoluble compounds thermodynamically. The dissolving 2) Complex reaction of M with OH
process for insoluble compounds is common in
M+iOH=M(OH)i (i=1, 2, 3, , y) (5)
hydrometallurgical and chemical fields. Studies about
[M(OH) i ]
ligand selection for dissolving the insoluble compound E (OH )
have not been reported in any of the studies published,
i
[M][OH  ]i
only some studies[1113] about leaching insoluble The complexation of A with M can be neglected
compounds with specific ligand were reported. without addition of A. Thereby, the total concentration of
In this work, the thermodynamic equilibrium of M can be expressed as
MaAm (insoluble compounds) dissolved by ligand in
x y
aqueous solution was analyzed. It is found that the
[M]T [M](1  E Li [L]i  E (OH)i [OH  ]i ) (6)
independent complexation of the ligand with the metal i 1 i 1
ion M is a key factor to dissolve MaAm. Other factors
could be simplified in a supposed ideal state. In this ideal 2.1.3 Equilibrium of A
state, the improper ligands could be directly rejected The protonation of A occurs if A is a weak acid
during primary selection, while the remained ligands radical in the solution:
could be selected carefully using the critical selection A+iH=HiA (i=1, 2, 3, , z) (7)
method in which all factors were considered. This ligand [H i A]
selection methodology provided fundamentals for E Hi A
[A][H  ]i
studying new leaching reagents in hydrometallurgy.
For the sake of simplification, redox reaction of The total concentration of A can be expressed as
metal ions and the probable charge were not discussed in z
this work. The insoluble compounds were symbolised as [A]T [A](1  E AHi [H  ]i ) (8)
i 1
MaAm, and the ligand was symbolized as L. For metal
ion or ligand concentration in aqueous solution, there are 2.1.4 Equilibrium of L
two expressions, the total concentration and free The protonation of L can be described as
concentration, which are unified as [M]T and [M],
L+iH+=HiL (i=1, 2, 3, , q) (9)
respectively.
[ H i L]
E LHi
2 Thermodynamic equilibrium and calcula- [L][H  ]i
tion According to Eqs.(4) and (9), the total
concentration of L can be expressed as
2.1 Thermodynamic equilibrium
x q
2.1.1 Solubility equilibrium of MaAm
[L]T [M] i E Li [L]i  [L](1  E LHi [H + ]i ) (10)
The solubility equilibrium of MaAm is the basis of i 1 i 1
complex-leaching process. The corresponding reaction is
as follows: 2.1.5 Dissociation equilibrium of H2O
In aqueous solution, there is always the following
MaAm=aM+mA (1) equilibrium:
Its solubility product constant can be written as Kw=[H+][OH] (11)
a m
Ksp=[M] [A] (2) Kw is a constant when the temperature and pressure are
According to Eq.(1), there will be given.
m
[A]T [M]T (3)
a 2.2 Calculation
2.1.2 Equilibrium of M There are eight unknown numbers containing [M]T,
The formation of polynuclear complex and [M], [L]T, [L], [A]T, [A], [OH], [H+] in Eqs.(2), (3), (6),
mixed-ligands complex were not considered in the (8), (10) and (11). Constants in these equations can be
dissolution of MaAm, so reactions in aqueous solution obtained in handbooks of thermodynamic data or by
will be simplified as follows: calculation. While the leaching conditions, such as the
1) Complex reaction of M with L pH value and [L]T value, are fixed, the other six
1150 YANG Tian-zu, et al/Trans. Nonferrous Met. Soc. China 20(2010) 11481153
unknown numbers can be calculated theoretically. This is Eq.(15) can be written as
a methodology for calculating solubility of MaAm.
Ksp {( E Li ) max [L]i }a a a mm S a  m (16)
YANG and QIU[14] introduced the similar method.
Obviously, the solubility calculated by this method is a From Eq.(16), following expression can be
comprehensive action of all the factors. obtained:
1 m am

3 Ligand selection ( E Li ) max [L]i K sp a am a S a (17)

It is known to all that there are multiple choices to Inserting Eq.(12) into Eq.(14), an equation can be
select ligands which can complex with the metal ion M. deduced as follows:
It is necessary to select ligands (or leaching reagents) [L]TiaS=[L] (18)
before conducting experiments to recover valuable metal
M in oxide ores. Inserting Eq.(18) into Eq.(17), (Li)max can be
described as
1 m am
3.1 Primary selection 
a am a S a
K sp
3.1.1 Independent complexation of ligand ( E Li ) max (19)
It is said that the solubility of MaAm in L-H2O ([L]T  iaS )i
system which has been introduced in section 2.2 is a In Eq.(19), ( E Li ) max can be constrained in a range
comprehensive action of all the factors. Actually, under a with the constraint of [L]T. Deducing the range of
certain condition, some of the factors that have little ( E Li ) max by discussing the range of [L]T using Eq.(19),
influence on the solubility MaAm can be neglected for so, three conditions can be deduced as a result.
simplifying the calculation. Especially in selecting ) 0[L]TiaS1, (Li)max must satisfy
ligands, this simplification is necessary and can make
1 m am
primary selection efficient. 
( E Li ) max Ksp a am a S a
To determine whether a ligand is suitable for
complex-leaching, it is necessary to exhibit its ) 1[L]TiaS10, ( E Li ) max must satisfy
combining ability completely. Otherwise, the reason why
the insoluble compound cannot be dissolved in the 1 m am

a am a S a 1 m am
solution will be confused. Supposed an ideal state in the Ksp 
( E Li ) max Ksp a am a S a
system, there is none but the independent complexation 10i
of L with M. The total concentration of L is enough to
) 10[L]TiaS100, ( E Li ) max must satisfy
ensure that the metallic ions M are combined to form the
most stable complex with L. In this state, the insoluble 
1 m am

1 m am
Ksp a am a S a Ksp a am a S a
compound MaAm will be leached certainly by an
(Li)max
arbitrary ligand which can complex with M. The 10 2i
10i
consumption of the ligand (the total concentration of L)
can be a criterion for ligand section. From the view of mathematics, the range of [L]T
3.1.2 Derivation in ideal state must contain [L]Tias0, [L]Tias100. In practice,
In the ideal state, the cumulative stable constant of the range of [L]Tias0 is not existent, and the range of
the complex can be written as ( E Li ) max . Setting the [L]Tias100 has no meaning to dissolve MaAm in so
solubility of MaAm as S, there will be equilibrium high concentration of ligands. While doing primary
equations as follows: selection, ligands whose ( E Li ) max satisfies condition
should be selected priorly, then condition, and the last
[M]T aS [M](1  (ELi )max [L]i ) | [M](ELi )max [L]i (12)
one is condition. Ligand whose ( E Li ) max does not
satisfy any one of the three conditions can be deserted
[A]T=[A]=mS (13)
directly. In addition, the total concentration of L can be
[L]T [M]i ( E Li ) max [L]i  [L] (14) calculated approximately as
1
According to Eqs.(12)(13), there will be 
1 m am i
Ksp a am a S a
[M]a (( E Li ) max [L]i ) a [A]m a a S a mm S m (15) > L@T  iaS (20)
( E Li ) max
According to solubility product rule of MaAm,
YANG Tian-zu, et al/Trans. Nonferrous Met. Soc. China 20(2010) 11481153 1151
3.2 Critical selection 4.1 Primary selection process
The remained ligands that had been selected by At 298 K, the solubility product constant of ZnCO3
primary selection should be selected carefully in this is Ksp=11010. Given that S=0.469 mol/L ([Zn2+]T=30
section. According to the calculation method in section g/L), the complex levels i are 14. The requirements of
2.2 with fixed value of pH and [L]T, the other unknown ( E Li ) max are given in Table 1. Part of the common
numbers can be calculated from the six equilibrium inorganic ligands and amino acidic ligands was
equations. Drawing a 3D graph using pH, [L]T, and [M]T investigated, and the results are given in Table 2.
as coordinates, the change tendency of [M]T can be Table 2 shows that ( E Li ) max of ligands Cl, SCN,
represented apparently with the change of pH and [L]T. SO4 , S2O32 and aminomalonic acid does not satisfy
2

The ligand should be finally determined in any of the three conditions, so they can be deserted
thermodynamics from the analysis of the 3D graph. In directly. ( E Li ) max of inorganic ligands OH, NH3, CN
addition, the distribution of M and L can help us to and P2O74 satisfy condition. It seems that they all can
analyze the affections of all the factors in dissolving be remained for the critical selection. NH3 and CN
process. which are toxic to human beings and environment will be
Actually, factors that affect ligand selection are deserted. OH and Zn2+ are combined together to form its
variable. Factors such as the combining ability of the 4th complex which needs the total concentration of OH
ligand with impurities, the price of the ligand, and the to be above 1.876 mol/L. Meanwhile, SiO2 in the ore can
environmental factors of the ligand which are commonly be dissolved into the solution at this concentration of
used in hydrometallurgy need to be considered during OH, which causes more consumption of OH. So, the
selection. remained ligand is P2O74.
All the amino acidic ligands seem to be remained
4 Case application except for aminomalonic acid ligand. It is known that the
price of organic agents is generally expensive. The
A sample of a low-grade zinc oxide ore, needs to be economic factors should be adequately considered while
leached for recovery of valuable metal Zn. The main carrying on the primary selection of these amino acidic
phase of Zn is smithsonite (ZnCO3) in the sample, as ligands. While the specific price of these ligands is
such we take ZnCO3 as the insoluble compound for unknown, according to Eq.(20), ligand whose ( E Li ) max
ligand selection. satisfies the conditionand the complex level is lower

Table 1 Requirements of ( E Li ) max composing certain level complex


Level Condition Condition Condition

1 lg ( E Li ) max 9.34 8.34lg ( E Li ) max 9.34 7.34lg ( E Li ) max 8.34


2 lg ( E Li ) max 9.34 7.34lg ( E Li ) max 9.34 5.34lg lg ( E Li ) max 7.34
3 lg ( E Li ) max 9.34 6.34lg ( E Li ) max 9.34 3.34lg lg ( E Li ) max 6.34
4 lg ( E Li ) max 9.34 5.34lg ( E Li ) max 9.34 1.34lg lg ( E Li ) max 5.34

Table 2 Results of primary selection


L Level lg ( E Li ) max Result L Level lg(Li)max Result
OH 4 14.8 Glycine(HL) 3 12.33
NH3 4 9.46 Alanine(HL) 3 10.57

Cl 2 0.61 DL-2-aminobutanoic acid (HL) 2 8.65

CN 4 19.62 2-amino-2-methylpropanoic(HL) 2 8.60

SCN 4 1.60 DL-2-amino-3-butenoic acid(HL) 2 8.86
4-
P2O7 2 11.00 -alanine(HL) 3 10.40
2
SO4 1 2.30 Aminomalonic acid(H2L) 1 6.48
2
S2O3 1 2.29 Aspartic acid(H2L) 2 10.15
Valine(HL) 3 10.78 Glutamic acid(H2L) 3 9.80
Serine(H2L) 3 11.91 Homoserine(H2L) 2 7.97
IDA(H2L) 2 12.52 Threonine(H2L) 2 8.66
1152 YANG Tian-zu, et al/Trans. Nonferrous Met. Soc. China 20(2010) 11481153
can be selected priorly. So, the remained ligands are IDA
and Aspartic acid.

4.2 Critical selection process


Taking IDA (C4H7O4N iminodiacetic acid) as an
example for critical selection, the ligand of IDA can be
written as Ida2. The thermodynamic data[1517] are
given in Table 3.

Table 3 Thermodynamic data of related species at 298 K


Species lgi Species lgi Species lgi

Zn(Ida) 7.24 Zn(OH)3 14.14 HIda 9.34
Zn(Ida)22 12.52 Zn(OH)42 17.66 H2Ida 11.95
Zn(OH)+ 4.40 HCO3 9.57 H3Ida+ 13.77
Fig.3 Distribution of Ida2 with pH
Zn(OH)2(aq) 11.30 H2CO3(aq) 15.59

Unknown numbers were calculated and a 3D graph


(Fig.1) was given by MATLAB software. When the total
concentration of the ligand is 1.0 mol/L ([Ida2]T=1.0
mol/L), the distributions of Zn2+, Ida2 and CO32 are
represented in Figs.24, respectively. The distribution is
described as its concentration that occupied in the total
concentration. This helps us to understand Fig.1 better.

Fig.4 Distribution of CO32 with pH

Fig.1 shows that the [Zn2+]T decreases with the


increase of pH value between 4 and 5. While in Fig.2
with pH of 45, the distribution of free Zn2+ decreases,
meaning that acid-leaching action of ZnCO3 decreases
with the decrease of acidity. While in Fig.3 with pH of
45, the distribution of HIda increases, which causes
the complexation of Ida2 with Zn2+ decreasing. Because
Fig.1 Tendency of [Zn2+]T with pH and [Ida2]T of these two decreasing actions, the [Zn2+]T decreases.
Fig.1 shows that the [Zn2+]T increases with the
increase of pH value between 5 and 9.6, and then
decreases slightly till pH nearly reaches 11. [Zn2+]T
approaches the highest value when pH reaches 9.6. Fig.2
shows that Zn(Ida) decreases and Zn(Ida)22 increases till
pH=7. In the pH range of 711, above 99% of Zn are
Zn(Ida)22. In Fig.3, HIda decreases and Zn(Ida)22
increases strongly from pH 5 to 9; from pH 9 to 11,
above 98% of Ida2 are combined with Zn2+ as
Zn(Ida)22.
From Figs.2 and 3, it seems that the [Zn2+]T will not
change much from pH 9 to 11. In fact, after the pH value
approaches nearby 9.6 in Fig.1, [Zn2+]T decreases slightly.
The change of this decrease can be explained in Fig.4. In
Fig.2 Distribution of Zn2+ vs pH Fig.4, the protonation of CO32 is dominant when pH
YANG Tian-zu, et al/Trans. Nonferrous Met. Soc. China 20(2010) 11481153 1153
9.6, which is promotional to dissolve ZnCO3; after pH of the ligand is existent in practice, and the theoretical
approaches 9.6, the free CO32 becomes dominant. derivations in the ideal state are reliable.
[CO32] increases dramatically when pH9.6, which
causes the decline of [Zn2+] because of solubility product References
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