Hydrometallurgy 169 (2017) 219–228

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Hydrometallurgy

journal homepage: www.elsevier.com/locate/hydromet

Selective leaching of zinc from blast furnace dust with mono-ligand and
mixed-ligand complex leaching systems
Duchao Zhang, Xinwang Zhang, Tianzu Yang ⁎, Shuai Rao, Wei Hu, Weifeng Liu, Lin Chen
School of Metallurgy and Environment, Central South University, Changsha 410083, China

a r t i c l e i n f o a b s t r a c t

Article history: The nonferrous metals in blast furnace dust, especially zinc, which used to be categorized as hazardous compo-
Received 30 August 2016 nents for blast furnace, are worthy of recovery in this economy. In this paper, a novel processing for extracting
Received in revised form 23 December 2016 zinc from blast furnace dust by using a coordination reaction between the organic ligand and zinc ions was pro-
Accepted 1 February 2017
posed. When blast furnace dust was leached in a 0.2 M iminodiacetic acid (Ida) solution at 20 °C for 2 h with a
Available online 05 February 2017
liquid-to-solid ratio of 10 mL/g, the leaching rates of zinc and iron were 62.78% and 6.07%, respectively. To accom-
Keywords:
plish the maximum separation of zinc from iron during the leaching process, a mixed-ligand complex leaching
Blast furnace dust system consisting of Ida as the primary ligand and ammonium as the secondary ligand was developed. The opti-
Iminodiacetic acid mal conditions for the leaching process with a mixed-ligand complex leaching system were investigated. We
Complex-leaching found that 65.58% of zinc was extracted by the solution with Ida:NH4Cl:NH3·H2O at 0.2:2:2 M and a 20:1 liq-
Zinc uid-to-solid ratio at 40 °C for 2 h.
Iron © 2017 Elsevier B.V. All rights reserved.

1. Introduction
Blast furnace dust is a byproduct of the ironmaking process and con-
sists of Fe, C, Si, some valuable metals, and so on. To recycle large
amounts of iron, blast furnace dust used to be sent directly back into
the blast furnace system as sintering raw material. However, in the
closed circulation process of recycling blast furnace dust, the gradual ac-
cumulation of volatile metals (Zn, Pb, etc.) will decrease the utilization
coefficient of the blast furnace and reduce blast furnace service life
(Mansfeldt and Dohrmann, 2004; Yang et al., 2009). Therefore, it is nec-
essary and valuable to separate the volatile metals from blast furnace
dust.
Blast furnace dust can be treated with pyrometallurgical and hydro-
metallurgical processes to recover metallic zinc. The Waelz process is
viewed as the leading and most representative pyrometallurgical meth-
od (Busè et al., 2014; Schneeberger and Antrekowitsch, 2011). In the
Waelz process, with coke as the reducing agent and fuel, ZnO and
ZnFe2O4 are reduced to gaseous metallic zinc and the gaseous metallic
zinc is then further oxidized and collected in the form of a zinc oxide
phase. Although the pyrometallurgical process can yield a high zinc re-
covery, it still has various shortcomings, including high energy con-
sumption, large capital investments and the production of harmful
greenhouse gases.
Various leaching agents are used in the hydrometallurgical process-
es for zinc extraction from blast furnace dust (Das et al., 2007; Huang et
⁎ Corresponding author.
E-mail address: tianzuyang@csu.edu.cn (T. Yang).
al., 2007; Soria-Aguilar et al., 2008). Zeydabadi et al. (1997) examined
blast furnace flue dust with H2SO4 as the leaching agent. The prelimi-
nary results of the investigation revealed that approximately 80% zinc
was extracted by a 1 M solution of H2SO4 with a residence time of
10 min and a solid-to-liquid ratio of 1/10 at room temperature. Steer
and Griffiths (2013) studied a leaching process for dust using organic
carboxylic acids to determine whether they were capable of extracting
high levels of zinc and low levels of iron. The results showed that high
levels of zinc and low levels of iron were extracted by a solution of
1 M prop-2-enoic acid. Furthermore, the use of a non-aqueous solvent
with prop-2-enoic acid was found to reduce the level of iron extraction
from 8.5% to 0.1%, without a detrimental effect on zinc extraction. A hy-
drometallurgical process whereby the sludge was leached under both
acid (HCl) and oxidizing conditions was investigated by Herck et al.
(2000). More than 90% of zinc leaching efficiency and 40% of the iron
leaching efficiency were obtained under the conditions of a pH below
1.5 and a redox potential above 650 mV. An acidic leaching process
can obtain a high zinc leaching rate, but undesired metals (i.e., iron, cop-
per, etc.) are also extracted into the waiting solution, and in addition,
the acidic solution is corrosive to the metallurgical instruments, leading
to a higher cost of recovery.
Ma Aiyuan et al. (2006) researched an ammonia leaching system
(ammonia/ammonium) for zinc recovery from blast furnace dust, pro-
ducing an extraction efficiency for zinc of up to 86.48% with a total am-
monia concentration of 5.0 mol/L and an ammonia/ammonium ratio of
1:1. With alkaline leaching, sodium hydroxide was preferred as the
leaching agent. The results showed that an alkaline solution could ex-
tract over 70% zinc from the dust and avoid iron and copper being

http://dx.doi.org/10.1016/j.hydromet.2017.02.003
0304-386X/© 2017 Elsevier B.V. All rights reserved.
220 D. Zhang et al. / Hydrometallurgy 169 (2017) 219–228
leached into the lixivium (Jha et al., 2001). Sodium hydroxide is selec-
tive for zinc dissolution but further development is required for metal
recovery from the sodium zincate solution by electrolysis. In addition,
the physical methods were applied for the direct removal of zinc or to
assist chemical processing to extract zinc from blast furnace dust
(Kiventerä et al., 2016; Ma, 2008; Vereš et al., 2011b; Vereš et al.,
2011a). Vereš et al. (2011b) treated the blast furnace sludge with micro-
wave-assisted leaching for the selective removal of zinc, and at micro-
wave heating at a power level of 160 W, the zinc recoveries were 10–
20% higher than the recoveries observed with conventional leaching.
For electric arc furnace dust (EAFD), which contains compounds
similar to blast furnace dust, zinc is separated from iron in the form of
gaseous chlorides by the method of chloridizing volatilization (Pickles,
2009). Aimed at solving the shortcomings of the pyrometallurgical
and hydrometallurgical processes, a hybrid process using thermal re-
duction followed by leaching for EAFD was investigated (Chairaksa-
Fujimoto et al., 2016). During this process, dust was roasted with calci-
um oxide to turn the insoluble and structurally stable zinc ferrite into
calcium ferrite. Simultaneously, zinc was separated from zinc ferrite
and oxidized to zinc oxide throughout the duration of the transition
process. Then, dust treated by calcium oxide was leached by an acidic
or alkaline solution to extract zinc into lixivium.
Recent reports have studied several organic ligands as leaching
agents for extracting zinc from different zinc-bearing materials, for ex-
ample, iminodiacetic acid for complex-leaching smithsonite (Yang et
al., 2010) and nitrilotriacetic acid for complex-leaching low grade zinc
oxide (Yang et al., 2016). Those studies indicated that the formation of
stable zinc complexes can improve zinc extraction.
Based on the coordination ability of the ligands with zinc ions and
iron ions, this paper selected iminodiacetic acid as the ligand to form
chelate complexes ([Zn(Ida)i]2-2i). A novel moderate mono-ligand com-
plex leaching system with an iminodiacetic solutions to leach the blast
furnace dust was proposed. Furthermore, because the mixed-ligand
complex has a greater stability constant than the mono-ligand complex
(Rao et al., 2015), ammonium chloride and ammonia were added to the
system to generate mixed-ligand complexes ([Zn(Ida)(NH3)i]) of zinc,
with Ida as the primary ligand and ammonium as the secondary ligand,
to explore the efficiency of complex-leaching for blast furnace dust. The
factors influencing zinc extraction in two complex-leaching systems, in-
cluding the ligand concentration, temperature, liquid-to-solid ratio,
time, and pH were studied in detail.
2. Experimental
2.1. Samples characterization and assays
The blast furnace dust used in this paper was supplied by a steel
plant in Yunnan, China. The following values of the chemical analysis
for the main elements were obtained. As shown in Table 1, the main el-
ements of the sample are Fe, O, C, Zn, Al, among others.
The mineralogical composition of the samples was determined by X-
ray diffraction (XRD) using a Rigaku, SmartLab Automatic Powder Dif-
fractometer with a graphite monochromator and Cu Kα radiation. Pow-
der samples were measured in the range of 10–90° 2θ at a scanning rate
of 10°/min.
The XRD pattern is shown in Fig. 1, and the blast furnace dust sample
consists of zincite (ZnO), franklinite (ZnFe2O4) or magnetite (Fe3O4),
hematite (Fe2O3), wustite (FeO), zinc silicate (Zn2SiO4) and quartz
Table 1
Composition of the blast furnace dust sample.
Component Zn Fe O Si Al Ca Pb
Wt% 5.10 38.49 20.39 4.66 2.57 2.25 0.94
Fig. 1. XRD pattern of the blast furnace dust sample.
(SiO2). The presence of franklinite in the sample is difficult to prove by
XRD because this material is isostructural with magnetite.
Using chemical analysis, the percentage of zinc present as different
phases (i.e., zinc oxide, zinc silicate, zinc sulfide and zinc ferrite) was
measured (Zhang, 1992). The results, consistent with the XRD pattern,
are shown in Table 2. The zinc oxide is the major phase, with a percent-
age close to 50%, and zinc silicate makes up 15.38% of the zinc. The sec-
ond-largest phase is zinc ferrite, which accounts for more than 28%. In
addition, a small amount of zinc sulfide is found in blast furnace dust
by chemical analysis.
The morphology, granularity and surface composition of the raw
material were detected by Scanning Electron Microscopy with Energy
Dispersive Spectrometry (SEM, JEOL, Ltd., JSM-6360LV). As shown in
Fig. 2, the particles of the blast furnace dust have various shapes and
sizes. The partial tiny bright particles visible with SEM, which are sup-
posed to be mixtures of metal oxides, i.e., Fe3O4, ZnO, and so on, are at-
tached to larger, dark particles, which are believed to be coke, according
to the EDS analysis.
The acidity was measured using a pH meter (Mettler Toledo, FE20).
2.2. Experimental procedure
Leaching experiments were performed in a beaker immersed in a
water bath with a thermostat that was equipped with a mechanical stir-
rer and a thermometer. After leaching, the waiting solution and residue
were obtained by vacuum filtration. Then, the leaching residue was
dried and weighted. The content of zinc and iron in the residue was de-
termined using the methods of EDTA titration and dichromate titration
respectively. The calculation of the formula for the zinc or iron extrac-
tion is given as follows:
 
wr
Extractionð%Þ ¼ 1‐  100%
wT
where wr is the weight of zinc or iron in the leaching residue and wT is
the total weight of the zinc and iron in the material being tested.
The effects of the concentration of the leaching agent, temperature,
leaching time, liquid-to-solid ratio, and pH value of the solution on the
Table 2
Percentages of different phases containing zinc.
C Phases Zinc oxide Zinc silicate Zinc sulfide Zinc ferrite
21.90 Percentage (%) 49.76 15.38 6.74 28.12
 D. Zhang et al. / Hydrometallurgy 169 (2017) 219–228 221

Fig. 2. SEM and EDS images of the raw blast furnace dust.

zinc and iron extractions with a stirring speed of 400 r/min were inves-
tigated to determinate the optimum conditions for zinc recovery. Each
zinc extraction is the average of two analysis results, and the extractions
under the optimal conditions are the average of three tests results.
To accomplish a thorough separation of zinc from iron, a mixed-li-
gand complex leaching system with Ida as the primary ligand and am-
monia as the secondary ligand was designed. The effects of the
concentration ratio of different ligands, temperatures, leaching times
and liquid-to-solid ratios on the zinc and iron extractions with a stirring
speed of 400 r/min were investigated to determinate the optimum con-
ditions for zinc recovery.
The stability constants of complexes indicate that glycine has a weak
ability to coordinate with zinc ions and iron ions, while nitrilotriacetic
acid and citric acid have strong coordination abilities with both zinc
ions and iron ions. Compared with the other ligands, iminodiacetic
acid is theoretically an excellent ligand for separating of zinc and iron
during leaching.
Four leaching experiments were carried out to explore the practical
leaching efficiencies of the above lixiviants. As shown as Fig. 3,
nitrilotriacetic acid and citric acid gave high levels of not only zinc but
also iron extractions, and iminodiacetic acid had a value for iron

3. Results and discussion

3.1. Determination of the ligand

Several organic agents, including glycine (gly), iminodiacetic acid

(Ida), nitrilotriacetic acid (NTA) and citric acid (cit), were explored as
lixiviants to treat blast furnace dust under the same conditions. The sta-
bility constants of complexes (MLi) composed of ligands and zinc ions or
iron ions are listed in Table 3 (Fang, 2007).

Table 3
Stability constants of complexes (MLi).

Ligands PH of Zn2+ Fe3+ Fe2+

solution at
lg(βZnL) lg(βZnL2) lg(βFeL) lg(βFeL2) lg(βFeL) lg(βFeL2)
0.2 M agent

gly 6.40 4.96 5.52 4.3 7.8 4.3 7.8

Ida 1.93 7.07 12.17 10.7 – 5.8 10.1
NTA 1.89 10.66 – 15.87 – 8.8 –
Fig. 3. Zinc and iron leaching efficiencies of different lixiviants (40 °C; 0.2 M lixiviant;
cit 1.85 11.4 – 25.0 – 15.5 –
liquid-to-solid ratio: 10 mg/L; stirring speed: 400 r/min; 2 h).
222 D. Zhang et al. / Hydrometallurgy 169 (2017) 219–228
Fig. 4. Diagram of the Fe3+ fraction in the mono-ligand complex leaching system.
extraction that was as low as glycine, with a high zinc extraction that
was close to NTA and cit. According to the pH values of the lixiviants
and the stability constants shown in Table 3, it can be inferred that the
decreases of the pH and the stability constants can improve the dissolu-
tion of both the zinc and undesired iron from blast furnace dust. For
these theoretical and practical reasons, iminodiacetic acid was chosen
as the ligand to extract zinc from blast furnace dust because of its mod-
eration and strong coordination ability with zinc.
3.2. Coordination leaching experiments
3.2.1. Thermodynamic analysis
In 0.2 M Ida solutions, the pH is 1.93. As shown in Eqs. (1) and (2)
(below), according to the Arrhenius theory, ZnO or Zn2SiO4 is dis-
solved by H+ that dissociates from Ida, with a dissociation constant
(ionization constant) of 10–9.38. Then, mono-ligand complexes are
formed, including [Zn(Ida)] and [Zn(Ida)2]2 −. The formation of zinc
complexes is believed to be beneficial to improve the zinc extraction.
Similarly, FeO and Fe2 O3 in the blast furnace dust also react with
Ida2 −, forming Fe(Ida)2-2i
i and Fe(Ida)+, respectively, as shown in
Eqs. (3) and (4).
 2−2i
þ 2H þ ¼ ZnðIdaÞi
2−
ZnO þ iIda þ H2 O
 4−4i
þ 4Hþ ¼ 2 ZnðIdaÞi
2−
Zn2 SiO4 þ 2i½Ida þ SiO2 ↓ þ 2H 2 O
Fig. 5. Diagram of the zinc ion fraction in the mono-ligand complex leaching system.
Fig. 6. Diagram of the Fe2+ fraction in the mono-ligand complex leaching system.
þ 2H þ ¼ FeðIdaÞi
2− 2−2i
FeO þ iIda þ H2 O ð3Þ
þ
þ 6H þ ¼ 2FeðIdaÞ þ 3H2 O
2−
Fe2 O3 þ 2Ida ð4Þ
3.2.2. Diagram of zinc ion fraction
To determine the additional quantity of Ida, according to the chem-
ical equation and stability constants of the zinc and iron complexes, the
software HYDRA/MEDUSA was used to draw diagrams of the zinc and
iron ion fractions in a mono-ligand complex leaching system
(Eriksson, 1979; Guśpiel and Riesenkampf, 1993; Puigdomenech,
2000).
The Fe3+ distribution proportion in different compounds varies with
the change of pH in the solution with Zn2+: Fe2+: Ida of 0.1:0.1:0.2 M,
as shown in Fig.4, suggesting that Fe3+ and Fe(Ida)+ are present only
when pH is below 2. When the pH rises above 2, all of the iron trans-
forms into Fe2O3. Therefore, there is no Fe3+ in the solution.
Fig. 5 reveals that the zinc distribution proportion for each com-
pound varies with the change of pH in the solution. The curves of the di-
agram show that as acidity decreases, complexes of Zn(Ida), Zn(Ida)2− 2
form in sequence. When the pH rises to 6.8, zinc oxide precipitates out
of the solution as a solid. Therefore, we suggest that the pH value of so-
lution after leaching should be controlled below 6.8 to minimize the
ð1Þ losses of zinc.
Fig. 6 shows that the Fe2+ distribution proportion in each compound
varies with the change of pH in the solution. The curves of the diagram
ð2Þ
Fig. 7. Effect of the lixiviant concentration on the zinc and iron leaching extractions. (40 °C;
liquid-to-solid ratio: 10 mg/L; stirring speed: 400 r/min; 2 h).
 D. Zhang et al. / Hydrometallurgy 169 (2017) 219–228
Fig. 8. Effect of temperature on the zinc and iron leaching extractions. (0.2 M Ida; liquid-
to-solid ratio: 10 mg/L; stirring speed: 400 r/min; 2 h).
show that as the acidity rises, complexes of Fe(Ida) and Fe(Ida)2−
2 form
in sequence. By comparing two figures, we can conclude that when the
pH rises to 7.3, ferrous hydroxide (Fe(OH)2) precipitates from the solu-
tion as a solid and Ida2− dissociates from Fe(Ida), leading to the rapid
increase of Zn(Ida)2−2 and the decrease of ZnO.
3.2.3. Effect of the iminodiacetic acid concentration
The effect of the iminodiacetic acid concentration on the zinc and
iron extractions was examined using six different initial concentration
fractions: 0.1 M, 0.2 M, 0.4 M, 0.6 M, 0.8 M, 1.0 M. As Fig. 7 shows, at
the low concentration of the iminodiacetic acid, the leaching process
for zinc and iron strongly depend on the acid concentration. The zinc ex-
traction is 57.75% in 0.1 M iminodiacetic acid solutions and increases to
64.48% in 0.2 M iminodiacetic acid solutions. When the concentration of
lixiviant ranged from 0.1 M to 0.4 M,the iron extraction increased from
4.01% to 10.34%. The further increase in the lixiviant has no obvious ef-
fect on iron extraction. Therefore, an iminodiacetic acid concentration of
0.2 M was chosen to investigate the other leaching parameters.
3.2.4. Effect of temperature
The effect of temperature on the zinc and iron extractions in a solu-
tion of 0.2 M Ida is shown in Fig. 8. The results show that approximately
62.78, 64.48, 64.90 and 64.85% of the zinc leaching rates were obtained
at temperatures of 20, 40, 60 and 80 °C, respectively. The iron extraction
Fig. 9. Effect of the leaching time on the zinc and iron leaching extractions. (40 °C; 0.2 M
Ida; liquid-to-solid ratio: 10 mg/L; stirring speed: 400 r/min).
223
Fig. 10. Effect of the liquid-to-solid ratio on zinc and iron leaching extractions. (40 °C;
0.2 M Ida; stirring speed: 400 r/min; 2 h).
was slightly boosted by the rise in temperature. The results indicate that
zinc extraction is nearly independent of temperature, and that 20 °C is
the optimal temperature for the separation of zinc from iron.
3.2.5. Effect of time
The changes in the zinc and iron extractions with time were investi-
gated. The results, shown in Fig. 9, indicate that the reaction between
zinc and the ligand is faster than the reaction between iron and the li-
gand. The slope of the curve indicates that the initial leaching speed of
zinc gradually decreases, and then the reaction is then complete after
2 h. The leaching speed of iron increases marginally at the beginning
of leaching, gradually decreases from 1 h to 3 h, and finally reaches a
plateau. Hence, the reaction time should preferably not exceed 2 h.
3.2.6. Effect of the liquid-to-solid ratio
To investigate the influence of the liquid-to-solid ratio on the disso-
lution of blast furnace dust, experiments were carried out in solutions
under different conditions of the liquid-to-solid ratio (2, 5, 8, 10, 20,
40 g/mL). As Fig. 10 shows, the extractions of zinc and iron increase as
the liquid-to-solid ratio increases. The amount of extracted zinc and
iron reach the peak value when the liquid-to-solid ratios are over 10
and 20 mL/g, respectively. Therefore, the most appropriate liquid-to-
solid ratio is 10 mL/g.
Fig. 11. Effect of the value of pH on the zinc and iron leaching efficiencies. (40 °C; 0.2 M Ida;
liquid-to-solid ratio: 10 mg/L; stirring speed: 400 r/min; 2 h).
224 D. Zhang et al. / Hydrometallurgy 169 (2017) 219–228

Fig. 14. Diagram of the zinc ion fraction in the mixed-ligand complex leaching system.
Fig. 12. XRD pattern of the residue leached by a solution of 0.2 M Ida,10:1 liquid-to-solid
ratio, at 20 °C for 2 h.
between iron and Ida, almost no iron was transferred into solution by
leaching when the pH value was over 5.

3.2.8. The leaching test under the optimal conditions

3.2.7. Effect of the pH value
The effect of the pH value on the leaching efficiencies of zinc and iron
was studied over the range of 2 to 8 under constant conditions, and the
results are shown in Fig. 11. Increasing of the pH value by adding sodi-
um hydroxide brings the leaching rate of zinc down gradually because
the reduction of the concentration of hydrogen ions makes the reaction
of Eqs. (1) and (2) difficult. However, the formation of complexes (ZnLi)
accounts for the zinc extraction over 50%. For iron, the leaching rate fell
sharply with the rise of the pH value. Practically, due to the low solubil-
ity product of iron and hydroxyl ions, and the weak coordination ability
Based on the above discussions, we can summarize that the optimal
conditions for leaching blast furnace dust with a mono-ligand complex
system is that 0.2 M of the iminodiacetic acid, 20 °C of temperature,
10 mL/g of the liquid-to-solid ratio, and 2 h of the leaching time. The ex-
tractions of zinc and iron were 62.78% and 6.07%, respectively.
3.2.9. The waiting solution at the optimal conditions
After the leaching test under the optimal conditions, the waiting so-
lution was obtained and contained 3.20 g/L Zn and 2.70 g/L Fe. In addi-
tion, there were 0.57 g/L Pb in the solution.

Fig. 13. SEM and EDS images of the residue leached by a solution with 0.2 M Ida, 10:1 liquid-to-solid ratio, at 20 °C for 2 h.
 D. Zhang et al. / Hydrometallurgy 169 (2017) 219–228 225

Table 4
Stability constants of mixed-ligand complexes.

Zinc complexes Zn(Ida)(NH3) Zn(Ida)(NH3)2 Zn(Ida)(NH3)3

lg(βZn(Ida)(NH3)i) 9.42 11.02 12.01

3.2.10. XRD pattern of leaching residues by iminodiacetic acid

The phases of the leaching residue obtained by the leaching experi-
ment under the optimal conditions were investigated by an X-ray dif-
fractometer, and the result is shown in Fig. 12. By contrastive analysis
of the XRD patterns of the raw blast furnace dust and treated dust, we
can see that the phase of zinc oxide disappeared, suggesting that ZnO
and Zn2SiO4 were dissolved into the leaching solution. Although the dif-
fraction peaks of magnetite and hematite can still be observed, their dif-
fraction peak intensities were obviously decreased, demonstrating that
the magnetite and hematite were partially dissolved. Fig. 10 shows that
the diffraction peak of zinc ferrite remains the same, which reveals that
the leaching agent was incapable of destroying the structure of zinc fer-
rite, explaining why zinc extractions are always lower than 70%. Fig. 16. Effect of temperature on the zinc and iron extractions. (Ida:NH4Cl:NH3·H2O of
0.2:2:2 M; liquid-to-solid ratio: 10 mg/L; stirring speed: 400 r/min; 2 h).

3.2.11. Scanning electron microscope (SEM) and energy dispersive spec-

trometer (EDS) analysis
Imaging using backscattered electron (BSE) with SEM and analysis
of the phases in the leached residue using EDS produce much clearer
pictures, as shown in Fig. 13.
Comparing Fig. 13 and Fig. 2 at the same magnification, we can con-
clude that the particle size becomes generally smaller after 2 h of
leaching. The zinc content of bright particles in Fig. 10 decreases re-
markably in contrast to the raw dust, indicating that ZnO is probably
dissolved during leaching. The smaller, very bright particles (Fig.
13(c)) are regarded as zinc ferrite (ZnFe2O4) due to the high Zn, Fe,
and O contents.
3.3. Experiments with a mixed-ligand complex leaching system
Based on the above discussions, we can conclude that the separation
of zinc and iron from blast furnace dust is probably controlled by the
acidity of the leaching solution. Hence, ammonium chloride and ammo-
nia were added into the system to create a buffer solution to control the
pH. In addition, because ammonia, Ida and zinc are able to generate
mixed-ligand complexes ([Zn(Ida)(NH3)i]) that have greater stability
constants than the mono-ligand complex, we can also avoid a decrease
in the zinc extraction. The factors influencing zinc extraction in the
mixed-ligand complex leaching systems, including the concentration
ratio of Ida:NH4Cl:NH3·H2O, temperature, liquid-to-solid ratio and
time, were studied.
Fig. 14 presents a diagram of the zinc ion fraction in a mixed-ligand
complex leaching system, and the Figure shows that zinc ions can form
mono-ligand complexes and mixed-ligand complexes with
iminodiacetic acid and ammonia in the solution with Zn2 +: Ida: NH3
of 0.1:0.2:4 M. The stability constants of the mixed-ligand complexes
are listed in Table 4. In that solution, when the pH is less than 3.0, the
free zinc ion accounts for most of the total zinc concentration. The
mono-ligand complexes ([Zn(Ida)] and [Zn(Ida)2]) become the pre-
dominant species when the pH is between 3.0 and 8.0. Then, the
mixed-ligand complexes ([Zn(Ida)(NH3)i]) emerge and gradually be-
come the major species. No zinc oxide appears until the pH increases
to 12.5. Therefore, the waiting solution obtained by the mixed-ligand
complex leaching system can be controlled over a wider range of pH
value. Because ammonia and ammonium chloride (1:1) can make up
the buffer solution with the pH maintained at approximately 8.5, the
zinc complexes of Zn(Ida)2− 2 , Zn(Ida)(NH3)2 and Zn(Ida)(NH3)3 are ex-
pected to be the major zinc complexes. At the same time, iron oxides
would not react with the leaching solution, but would remain in the

Fig. 17. Effect of the leaching time on the zinc and iron extractions. (40 °C;
Fig. 15. Zinc and iron extractions with different concentration ratios of Ida:NH4Cl:NH3·H2O of 0.2:2:2 M; liquid-to-solid ratio: 10 mg/L; stirring speed:
Ida:NH4Cl:NH3·H2O. (40 °C; liquid-to-solid ratio: 10 mg/L; stirring speed: 400 r/min; 2 h). 400 r/min).
226 D. Zhang et al. / Hydrometallurgy 169 (2017) 219–228
residues. The equations for the reactions during the leaching process are
shown in Eqs. (5) and (6).
 
þ iNH 3 þ H 2 O ¼ ZnðIdaÞðNH 3 Þi þ 2OH −
2−
ZnO þ Ida
2−
Zn2 SiO4 þ 2½Ida þ2iNH 3 þ 2H 2 O
¼ 2 ZnðIdaÞðNH 3 Þi þ SiO2 ↓ þ 4OH −
3.3.1. Effect of the lixiviants ratio
According to the calculation for the coordination model between Ida
and ammonia, four concentration ratios of Ida, ammonium chloride and
ammonia liquor (Ida:NH4Cl:NH3·H2O) were studied. The results,
shown in Fig. 15, demonstrate that the zinc extraction with a concentra-
tion ratio of 0.2:2:2 is the largest and that of 0.1:1:1 dissolves the min-
imal zinc. It is noted that in the leaching test with the ammonium
chloride/ammonia system with NH4Cl:NH3·H2O of 2:2 M, 53.97% of
the zinc extraction were achieved. Combining with the stability con-
stants of Zn(NH3)i and Zn(Ida)i(NH3)i, we can conclude that the addi-
tion of Ida can improve the zinc extraction theoretical and practically.
As expected, almost no iron is extracted by each solution of the
mixed-ligand complex leaching system. The concentration ratio of
0.2:2:2 was chosen in later experiments.
3.3.2. Effect of temperature
The effect of temperature was studied at 20, 40, 60 and 80 °C at a
concentration ratio of 0.2:2:2 M. The results are shown in Fig. 16. The re-
sults clearly indicate that the elevated temperature slightly improves
the zinc extraction, with approximately 57, 62, 65 and 67% of the zinc
extractions obtained at 20, 40, 60 and 80 °C, respectively, after 2 h of
leaching. When the temperature is 80 °C, a small amount of iron is
also transferred into the leaching solution. From an economic perspec-
tive, the optimum value of temperature of approximately 40 °C is suit-
able for the leaching process.
3.3.3. Effect of time
The zinc extraction curve in Fig. 17 shows that the changing trends
in the zinc extraction in a mixed-ligand complex leaching system are
similar to the trends in the mono-ligand complex leaching system.
After 2 h of leaching, the zinc leaching rate tends to stabilize, and in-
creases to 65.58%. The iron extraction curve shows that extending the
leaching time can dissolve a small amount of iron, which is undesirables.
Fig. 18. Effect of the liquid-to-solid ratio on the zinc and iron extractions. (40 °C;
Ida:NH4Cl:NH3·H2O of 0.2:2:2 M; stirring speed: 400 r/min; 2 h).
ð5Þ
ð6Þ
Fig. 19. The XRD pattern of the residues leached by the solution with Ida:NH4Cl:NH3·H2O
of 0.2:2:2 M, 20:1 liquid-to-solid ratio, at 40 °C for 2 h.
Thus, an appropriate leaching time of 2 h is favorable for higher zinc ex-
traction and lower iron extraction.
3.3.4. Effect of the liquid-to-solid ratio
The effect of the liquid-to-solid ratio on zinc extraction was studied.
The results are shown in Fig. 18 and indicate that the liquid-to-solid
ratio has a significant effect on zinc extraction. When the liquid-to-
solid ratio is between 2 and 20 mL/g, the zinc extraction rises signifi-
cantly from 11.71% to 65.58%. Raising the liquid-to-solid ratio does not
extract more iron. Hence, the optimal liquid-to-solid ratio is 20 mL/g.
3.3.5. The mixed-ligand complex leaching test under the optimal condition
Based on the above discussions, the maximum zinc had been
leached at the conditions that Ida:NH4Cl:NH3·H2O of 0.2:2:2 M, 20:1
of liquid-to-solid ratio, at 40 °C for 2 h. The extraction of zinc was
65.58%, while almost no iron was extracted by mixed-ligand complex
leaching system.
3.3.6. Analyze of pregnant solution at the optimal condition
According to the results of ICP analysis, the solution obtained by
mixed-ligand complex leaching test had 1.67 g/L Zn, 0.0297 g/L Fe and
0.27 g/L Pb.
3.3.7. Characteristics of residues leached by solution with mixed-ligand
complex leaching system
The XRD pattern of residues leached by the solution with the mixed-
ligand complex leaching system is shown in Fig. 19. In addition, the dis-
tribution of the phase containing zinc in the residues was measured,
shown in Table 5. We can conclude from Fig. 19 and Table 5 that the
most of the oxides containing zinc, including ZnO and Zn2SiO4, were dis-
solved into the leaching solution. The zinc sulfide and zinc ferrite had
not been leached due to their insolubility or stable structure.
Fig. 20 is the SEM and EDS images of the residues leached by the so-
lution with Ida:NH4Cl:NH3·H2O of 0.2:2:2 M, 20:1 liquid-to-solid ratio,
at 40 °C for 2 h. We can infer that the mixed-ligand complex leaching
system leaching testes make the dust particles become smaller like
the testes of the mono-ligand complex leaching system do. Compared
Table 5
Percentages of different phases containing zinc in residues leached by the solution with
Ida:NH4Cl:NH3·H2O of 0.2:2:2 M, 20:1 liquid-to-solid ratio, at 40 °C for 2 h.
Phases Zinc oxide Zinc silicate Zinc sulfide Zinc ferrite
Percentage/% 0.00 1.09 19.08 79.83
 D. Zhang et al. / Hydrometallurgy 169 (2017) 219–228
Fig. 20. SEM and EDS images of the residues leached with Ida:NH4Cl:NH3·H2O of 0.2:2:2 M. 20:1 liquid-to-solid ratio, at 40 °C for 2 h.
to Fig. 13, there are fewer tiny particles on the surfaces of the large
particles.
4. Conclusion
From the results of the experiments and discussions of the results,
we can reach the following conclusions:
1. Iminodiacetic acid is the ideal leaching agent for recovering zinc from
blast furnace dust because of its moderate characteristics and strong
coordinating ability with zinc.
2. Both the mono-ligand and mixed-ligand complex leaching systems
of iminodiacetic acid are suitable for leaching blast furnace dust.
The mixed-ligand complex leaching system is able to easily separate
zinc from iron, and after 2 h of leaching, 65.58% of zinc and almost no
iron were extracted in the solution with a lixiviant concentration
ratio of 0.2:2:2 M at a temperature of 40 °C.
3. Using the coordination between the ligands and zinc has proven to
be effective at extracting zinc from zinc oxide. However, the treat-
ment process of zinc ferrite in dust should be developed.
Acknowledgement
This study was financially supported by the National Basic Research
Programme of China (No. 2014CB643404), the National Natural Science
Foundation of China (No. 51504292) and the 2011 Joint Innovation Cen-
ter – “clean and effective utilization of strategic mineral resources”.
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