Hydrometallurgy 173 (2017) 250–257

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

Development of a combined solid and liquid wastes treatment integrated MARK

into a high purity ZnO hydrometallurgical production process from Waelz
oxide
N. Antuñano⁎, J.F. Cambra, P.L. Arias
Chemical and Environmental Engineering Department, University of the Basque Country (UPV-EHU), Alameda Urquijo s/n, 48013 Bilbao, Spain

A R T I C L E I N F O A B S T R A C T

Keywords: Electric Arc Furnace Dust (EAFD) is an important hazardous waste from the steel production industry, due to its
Sustainable metallurgy heavy metals content. It is recycled through a pyrometallurgical process to generate a Zn and Pb concentrate
Heavy metals stabilization called Waelz oxide. This concentrate can be processed hydrometallurgically in order to obtain high purity ZnO.
Ammonia removal But this hydrometallurgical process also generates as wastes different solid residues with high content of heavy
Clean technologies
metals and a liquid waste stream with significant concentrations of ammonia and heavy metals. This is why the
Waelz oxide
objective of this work is to design a process that can simultaneously treat these solid and liquid wastes. In the
Zinc oxide
developed process, an alkaline solution is used to leach solid residues so as to produce an inert final waste. After
filtration, the leaching liquor is mixed with the liquid waste in order to increase its pH and to enhance the
ammonia evaporation by air stripping. This stripped stream can be recycled to the leaching stage of the Waelz
oxide treatment process. Furthermore, the ammonia stripping precipitates the dissolved heavy metals as a zinc
concentrate that can be commercialized as a raw material for the metallic zinc production industry. Therefore,
the developed process reduces by more than half the wastes generation, increases the Zn recycling yield > 5%
and recovers > 75% of the needed ammonia for the fresh leaching liquor.

1. Introduction
Steel is one of the most widely used metallic materials in our
modern world, because of the adaptability and durability of its pro-
ducts. Hence, steelmaking industry produces approximately 1.6 billion
tons of steel every year to meet worldwide consumption demand. 40%
of the processed steel is obtained from recycled waste in electric arc
furnace (World Steel Association, 2014). During the melting of scrap in
the furnace, the electric arc furnace dust (called EAFD) is generated and
collected by bag filters or electrostatic precipitators (De Araujo et al.,
2014). In the most developed countries this dust is classified as ha-
zardous waste due to its toxic heavy metals content. Obviously, for
economic reasons and to prevent environmental impacts, this dust must
be treated in order to recycle part of its heavy metals (Gupta et al.,
1990; Orhan, 2005). An average steelworks facility generates approxi-
mately 15 kg of EAFD per ton of steel (Dutra et al., 2006).
Nowadays, Waelz process is acknowledged as the Best Available
Technology (BAT) in order to treat EAFD, according to Reference
Document for Non-Ferrous Metal Industries (Industrial Emission
Directive, 2010). The product of Waelz process, named Waelz oxide, is
a mix of mainly zinc and lead oxides with several impurities.
Waelz oxide is sold to zinc concentrator companies to produce high-
purity zinc products, basically, metallic zinc and zinc compounds such
as zinc oxide and zinc sulphate (International Lead and Zinc Study
Group, 2011). High-purity zinc oxide is the most produced and widely
used zinc compound. It is used in rubber vulcanization as a catalyst for
its manufacture. It is also employed in ceramics, paints, animal food,
pharmaceuticals and in many other products and processes. In addition,
special grade of zinc oxide has long been used in photocopiers. This
oxide is also used in varistors, providing protection against over-vol-
tages. ZnO market supposes 100,000 tonnes per year. It is fabricated
through three different technologies: French process, American process
and Hydrometallurgical process (Klingshirn, 2007). Even today, the
most used technologies are American and French processes (Pyr-
ometallurgical processes), although they require purer raw materials
(zinc ingot, zinc mattes, zinc ashes, and so on) on the contrary of the
Hydrometallurgical ones. This last alternative uses ammonium carbo-
nate and ammonia solutions as leaching liquors to purify Waelz oxide
and it has been investigated by different researchers (Núñez, 2005;
Meseguer et al., 1996; Ruíz et al., 2007).

⁎
Corresponding author.
E-mail address: nestor.antunano@ehu.es (N. Antuñano).

http://dx.doi.org/10.1016/j.hydromet.2017.09.002
Received 5 December 2016; Received in revised form 11 August 2017; Accepted 2 September 2017
Available online 04 September 2017
0304-386X/ © 2017 Elsevier B.V. All rights reserved.
N. Antuñano et al. Hydrometallurgy 173 (2017) 250–257

The main conclusion of these previous works is that a very pro-
mising ZnO production yield can be obtained from the hydro-
metallurgical treatment of Waelz oxide, but the ammonia and heavy
metals discharge and solid wastes disposal make impossible its in-
dustrial application. So, further research is required to get this process
closer to its industrialization.
Firstly, in this study a hydrometallurgical process to high-purity zinc
oxide production using ammoniacal solutions as leaching liquors was
optimized. Once zinc is dissolved from Waelz oxide with other im-
purities (i.e. iron, lead, cadmium and copper), these are eliminated
from the zinc solution through purification stage: i) via oxidation with
air (iron removal) and ii) via cementation with metallic zinc powder
(removal of other metallic impurities). The purified zinc solution is
precipitated through CO2 (g) injection at room temperature obtaining
zinc carbonate species. Then, it is calcined to yield zinc oxide of a high
grade (ZnO of purity higher than 99.0%). Nevertheless, the final in-
dustrial development must include the exhausted liquor recycling and
wastes treatment technologies. Therefore, the main aim of this work is
to develop a new chemical process, that combines solid and liquid re-
sidues treatment from the previously described ZnO hydrometallurgical
process, in order to achieve a technoeconomically feasible and en-
vironmentally benign technology to convert Waelz oxide into com-
mercial high-purity zinc oxide.
The solid wastes generated by the ZnO hydrometallurgical pro-
duction process stages (leaching, oxidation and cementation) are cate-
gorized as dangerous and hazardous industrial wastes (Boreiko, 1991).
The main problem of these waste products lies in their disposal due to
the high concentration of heavy metals such as cadmium, lead, chro-
mium, mercury and zinc. As these metals tend to bio-accumulate they
are extremely toxic even at low concentrations. For zinc dosses between
225 and 450 mg/day are considered as severe toxicity (World Health
Organization, 2011). Regarding the liquid waste stream generated in
this high-grade ZnO production process, pH, dissolved ammonia and
heavy metals content must be controlled. Ammonia can simultaneously
be in two forms at an equilibrium mostly governed by pH and tem-
perature. This forms are NH3 (un-ionized ammonia) and NH4+ (ionized
ammonia or ammonium). The sum of these two forms is called total
ammonia. The NH3 form is particularly harmful for aquatic organisms,
being limited its discharge. The maximum permissible concentrations of
metals in natural waters are recommended and regulated by several
environmental protection agencies for the human health. This implies
that they must be removed from industrial wastes streams. For this
reason, the intended combined process must allow to inertize the solid
residue, recovering the highest possible proportion of metals in order to
increase the metallic yield and profitability of the plant. In the same
way, dissolved ammonia in the exhausted liquor must be recovered so
as to reuse it as a reagent in the leaching liquor formulation. This re-
covery generates a zinc concentrate by-product from the liquid waste
treatment stage. Thus, this study deals with the design of solid and li-
quid hazardous wastes treatment process integrated in a hydro-
metallurgical plant producing high grade ZnO from Waelz oxide. This
improvement reduces environmental impact and increases techno-
economic viability of the zinc recycling. The developed technology
could be applied to other metallurgical processes with similar wastes (e.
g. Ni, Cu or Co via Sherritt Gordon Process).
hydroxide pellets pure (Panreac) as pH modifier.
All experiments were carried out in a 2 L glass reactor with me-
chanical stirring. The reactor worked in a thermostatic bath and it was
operated closed in order to avoid water losses by evaporation. An Orion
Star A329 Multiparameter apparatus was used as pH and temperature
controller. The pH control of the leaching stage was carried out auto-
matically by acid/alkali addition through a peristaltic pump controlled
by the A329. The ammonia stripping experiments were carried out in
the 2 liter glass reactor with mechanic stirring. In this case, the stirrer
was perforated in order to permit the gas injection. The gas was injected
from the laboratory compressed air line and using a Dwyer serie STFO
as a flowmeter. The reactor worked in a thermostatic bath and the cover
had a gas extraction system. The stripped ammonia was recovered in an
absorption reactor. Millipore ASME - MU High pressure filter, YT30-
142HW model, was used for solid/liquid separation so as to take the
samples which were analysed.
Chemical analysis of the used Waelz oxide sample and the generated
solid wastes and treated solid residues were carried out using a mi-
crowave acid digestion procedure and the subsequence analysis of the
metal contents with an ICP - AES Perkin Elmer 2000 - DV model. The
metallic ions concentrations in the liquid samples of the obtained zinc
liquors were also analysed by ICP - AES (Perkin Elmer 2000 - DV
model). Argentometry tritration (Crison 8661 Titromatic) was used to
measure the chloride concentration and a fluoride ion selective elec-
trode (Crison 9655) was used for fluoride analysis. Dissolved ammonia
was analysed using a high-performance ammonia ion selective elec-
trode (Orion Ammonia gas sensing electrode) and a carbon dioxide ion
selective electrode (Orion Carbon dioxide electrode 952BNMP) was
used in the analysis of total carbonates present in the liquid samples.
Zinc concentrate obtained in the ammonia recovery stage was also
analysed by X ray diffraction (using a Brucker D8 Advance
Diffractometer), equipped with a primary germanium monochromator
with Bragg-Brentano geometry and with a CuKα1 wave-length of
1.5406 Å. Thermogravimetric analysis was carried out using a
microThermogravimetric Analizer with small furnace TGA 2 Mettler
Toledo.
3. Results and discussion
3.1. Characterization of raw material and treated solid and liquid wastes
First of all, the patented industrial process to produce high-purity
zinc oxide from Waelz oxide, using aqueous solutions of ammonium
carbonate and liquid ammonia as leaching liquor (Alguacil et al., 1998),
was improved and optimized. In this work, all the hydrometallurgical
stages were further studied with the purpose of improving ammonia
recovery and final quality of the product (ZnO). In addition, ammonia
losses and energy consumption (new design without evaporation stage)
were minimized.
The characterization of the Waelz oxide used as raw material in this
study is shown in Table 1.
Table 1
Composition of Waelz oxide supplied by Befesa S.A.

Element Weigh (%) Element Weigh (%)

2. Materials and methods
Zn 55–58 Stotal 0.7–1.0
The Waelz Oxide sample under study (used as raw material) origi- Pb 7–10 F 0.15–0.18
Cd 0.3–0.5 Cl 4.5–6.1
nates from the BEFESA ZINC ASER S.A. plant (Spain) and it was used as Cr 0.1–0.3 Ni 0.03–0.12
received. Cu 0.2–0.6 Ctotal 1.0–2.0
The reactants used during the experimental works are ammonium Sn 0.1–0.2 FeO 5–7
carbonate (ACS grade, SIGMA-ALDRICH) and liquid ammonia 25% Al2O3 0.1–0.4 MnO 0.4–0.7
SiO2 0.5–1.5 Na2O 1.1–1.5
(ACS grade, SIGMA-ALDRICH) to prepare the leaching liquor, zinc
CaO 0.3–1.0 K2O 1.5–2
powder as cementation agent (pure, SIGMA-ALDRICH), CO2 gas MgO 1.5–2.5 Hg (ppm) 3–30
(ALPHAGAZ 2, AIR LIQUIDE) as precipitation agent and sodium

251
N. Antuñano et al.
In the studied high purity ZnO production process Waelz oxide is
leached in order to dissolve as much quantity of the contained zinc as
possible using ammonium carbonate as leaching liquor. The liquor
concentration and the operation conditions were optimized for the
leaching stage. The direct relation between ammonia liquid quantity
and the zinc recovery yield could be noticed following the main che-
mical reaction (Eq. (1)). But it is only possible in a specific range of pH
(9.5–11.5), because the ammonia zinc complexes have their highest
solubility values under these conditions. The total carbonates con-
centration generates a buffer effect in the liquor, which provides the
maintenance of pH inside the optimal limit. A larger quantity of car-
bonates permits a higher ammonia concentration in the leaching solu-
tion, increasing the zinc recovery (Lozano et al., 1999). The liquor
composition, leaching temperature and reaction kinetics were opti-
mized.
ZnO + 4 NH3 + H2 O ⇔ Zn(NH3 )4 2 + + 2 OH– (1)
After leaching stage, obtained zinc solution must be purified to
achieve the target quality in the final product. The goal of the pur-
ification stages is to remove the impurities from the leaching liquor,
trying to reduce as little quantity of dissolved zinc as possible.
Cementation is the most used purification method in zinc hydro-
metallurgy. In this process all metals with standard reduction potentials
(volts) lower than zinc (iron, nickel and chromium in this case) will not
be removed, decreasing the value of the final product. For this reason, it
is necessary to analyze an oxidation stage before the cementation
process.
In the zinc hydrometallurgy some oxidant agents are used to remove
the iron from the leaching liquors by precipitation. For example, in the
electrolytic zinc production process, MnO2 is the most commonly used
compound (Barakat et al., 2006; Koleini et al., 2004) due to protective
effect of Mn2 + on the aluminium cathodes. The hydrogen peroxide
(Baik et al., 2000) is an efficient oxidant, which does not incorporate
any impurity into the solution. But the use of H2O2 involves an ex-
haustive control of the pH adding chemical compounds, preferentially
at acid pH. Oxidant gases can be used also for oxidation process of zinc
hydrometallurgical liquors. After these considerations, the most proper
treatment for the obtained leaching liquors is an oxidation step using
oxygen from the atmospheric air. The air flow rate, oxidation tem-
perature and reaction kinetics were optimized.
O2 + 4Fe2 + + 10H2 O ⇔ 4Fe(OH)3 ( ↓ ) + 8H+ (2)
E = E° − (RT nF) ln([H+]8 PO2 [Fe2 +]4 )
E° = E°red − E°ox = 1.23 V − 0.77 V = 0.46 V
The last purification step to reach the target quality of the hydro-
metallurgical liquor is the cementation stage. The goal of this process is
to remove the remaining metallic impurities (after oxidation) dissolved
in the liquor. The operation is used to precipitate metallic ions (Men +)
from the solution onto another cementation agent that is more elec-
tropositive. Zinc metal itself is more electropositive than most of the
dissolved metal impurities (ΔE0 = Ei0 − E0Zn(II)/Zn(0) (V)), thus, it is
used as cementation agent. The cementation process inevitably occurs
in the presence of a surface scale, where the surface of the reducing
metal is covered by porous layers of the cemented metal. Therefore, the
porous cemented metal must be electronic conductive and so it favours
further dissolution of the reducing metal (Noubactep et al., 2010). In
addition, the oxidation of metallic zinc dust enriches the liquor and the
yield of the global process, following the main reactions of this step:
Zn0 (s) ⇔ Zn2 + (aq) + 2e− (3)
Men + (aq) + ne+ ⇔ Me0 (s) (4)
The zinc dust addition, cementation temperature and reaction ki-
netics were optimized. The result of the purification stages is ammo-
nium carbonate solution with a high concentration of zinc ions that
252
Hydrometallurgy 173 (2017) 250–257
must be recovered from the liquor. The adopted strategy in this case is
to recover the zinc in solid phase as zinc carbonate and zinc hydroxide
which will need a subsequent thermal treatment of these solids to ob-
tain the target ZnO. Several options exist to recover the dissolved zinc
from the liquor: evaporation, crystallization or precipitation. In this
case, chemical precipitation is selected because final product char-
acteristics make other options energetically unsustainable.
This chemical precipitation was carried out with CO2 (from Waelz
Furnace Flue-Gas) by absorption in the cementated liquor (as H2CO3
(aq)), so the pH of the solution decreases and also the zinc solubility.
The solubility of carbonates in the solution will be increased until it
exceeds the saturation conditions, so the dissolved zinc (M2 +) is going
to be recovered as zinc carbonate (Stumm et al., 1970). The injected
CO2 flow rate from the Waelz furnace flue-gas, precipitation tempera-
ture and reaction kinetics were optimized.
MCO3 ( ↓ ) ⇔ M2 + + CO32– (5)
MCO3 ( ↓ ) + H+ ⇔ M2 + + HCO3– (6)
MCO3 ( ↓ ) + H2 CO3 (aq) ⇔ M2 + + 2HCO3− (7)
MCO3 ( ↓ ) + H+ ⇔ M2 + + H2 CO3 (aq) (8)
After the recovery of dissolved zinc through precipitation in the
previous step as zinc carbonate, a thermal treatment is needed to re-
move water, carbon dioxide and other gases (because they are chemi-
cally bounded), in order to obtain the target product (Fig. 1). Therefore,
calcination stage was designed and optimized as a final step of this high
purity zinc oxide fabrication process, testing the influence of tem-
perature and residence time in the final quality and obtaining costs of
the target product.
ZnCO3 ·n H2 O (s) ⇔ ZnO (s) + CO2 (g) + n H2 O (g) (9)
88% of zinc recovery was reached in this optimized hydro-
metallurgical process (Fig. 2), obtaining ZnO with a purity above to
99% (0.06% Fe2O3, 0.09% Al2O3, 280 ppm F, 150 ppm Ni, 26 ppm Cu
and 5,6 ppm Pb). After this optimization, generated wastes at all stages
need to be characterized
This characterization is necessary to evaluate the toxicity of dif-
ferent residues that are generated during the production processes. In
this case, the hydrometallurgical process generates different solid re-
sidues and a liquid waste (the exhausted liquor). Solid wastes are
generated during the leaching stage and the following leaching liquor
purification stages (oxidation and cementation processes). The solid
residue from the leaching stage contains insoluble matter of the Waelz
oxide in the optimized ammoniacal solution used as leaching liquor.
The solid wastes from the purification stages are composed of several
metallic impurities removed from the leaching solution. As can be seen
in Table 2, these solid residues contain high concentrations of several
toxic heavy metals with different proportions depending on the process
where these wastes are generated.
These three waste streams were blended, in the proportions which
were generated, because the amount of oxidation and cementation solid
residues is small in comparison with the leaching residue (Fig. 2) in
order to design and optimize a single treatment adequate for the re-
sulting solid mixture. The chemical characterization of the blending of
generated residues is shown in Table 3.
On the other hand, the exhausted liquor of the production process,
after most of the dissolved zinc is recovered in the precipitation stage,
cannot be directly recycled and it must be treated for economic and
environmental reasons. Therefore, this liquid waste was characterized
in order to study an efficient process to remove the most hazardous
substances and at the same time, trying to obtain some marketable by-
product. The chemical characterization of the exhausted liquor is
shown on Table 4.
During the optimization of the hydrometallurgical stages all the
ammonia losses were measured in order to identify the recoverable
N. Antuñano et al.
Fig. 1. Thermogravimetric analysis of the precipitated product.
ammonia sources for spent liquor regeneration. The ammonia balance
of the hydrometallurgical processes (Fig. 3) shows that the 78.9% of
required ammonia in the leaching stage could be recovered. But 39.2%
of this ammonia has to be recovered from liquid phase in the exhausted
liquor. Therefore, a new process needs to be designed for the recovery
of this ammonia.
As indicated before, to produce industrially 600 kg of high-purity
zinc oxide per ton of fed Waelz oxide, 124 kg of solid residue and 5800 l
of liquid waste are generated. In Fig. 4, a simplified block-diagram of
253
Hydrometallurgy 173 (2017) 250–257
the developed process is represented. There can be seen liquid and solid
residues treatment step integrated in the hydrometallurgical process.
In the following sections the processes of this treatment will be
detailed.
3.2. Optimization of operation parameters
In the exhausted liquor the dissolved ammonia is present as am-
monium ions, NH4+, or as zinc ammonia complex ions. The stability of
Fig. 2. Flow sheet for the optimized high-purity
zinc oxide hydrometallurgical production pro-
cess.
N. Antuñano et al. Hydrometallurgy 173 (2017) 250–257

Table 2
Metallic composition of different solid residues generated in the high purity zinc oxide
production process.

Element Composition of the Composition of the Composition of

leaching solid residue oxidation solid cementation solid
(%) residue (%) residue (%)

Zn 16–20 55–60 20–25

Pb 46–52 2.5–5 42–46
Fe 5–7 0.5–1 0.1–0.25
Cu 0.1–0. 5 0.01–0.05 1–2
Mn 0.5–0.8 0.25–0.5 0.02–0.05
Cd 0.05–0.1 0.01–0.02 6–10
Sn 1–1.5 0.01–0.05 0.02–0.05

Table 3
Chemical composition of the blended solid residue.
Fig. 3. Total ammonia balance in the optimized high-purity zinc oxide production pro-
Element Zn Fe Pb Cd cess.

Composition (%) 24–26 5–6 40–45 0.8–1.25

transfer rate of ammonia from water to the gas phase (Heggemann
et al., 2001):
complex-formation reactions are modified by inducing pH variation. At
pH = 11.5–12 almost only dissolved ammonia (NH3 (aq)) is present in - The air-water surface tension
an aqueous solution. Under proper conditions this ammonia would be - The ammonia concentration gradient between gas stream and li-
recovered as a useful gas stream. In order to maximize the quantity of quor.
dissolved ammonia, an increase of exhausted liquor pH was carried out
with a sodium hydroxide aqueous solution. The stripping of this dis- The designed processes must combine the transformation of NH4+
solved ammonia was also conducted through air injection at controlled to dissolved ammonia and the stripping of this ammonia. The necessity
conditions. Thus, these modifications in the exhausted liquor will also of an alkaline solution in order to increase the pH of the exhausted
generate zinc recovery by precipitation, increasing the economical yield liquor was previously concluded. Thus, to develop an integrated pro-
and the efficiency of the recycling process (Table 5). cess, this required alkaline solution (to increase the pH of the exhausted
liquor) is previously used as leaching liquor of solid wastes.
- Main reactions in the liquor: The chosen alkaline liquor was a caustic soda aqueous solution. The
leaching experimental conditions were carried out at 25 °C, using a L/S
NaOH ⇔ Na+ + OH– (10)
ratio = 6 with contact time equal to 90 min in the stirred tank
NH 4 + + OH– ⇔ NH3 + H2 O (11) (700 rpm). The evolution of metals recovery and pH by increasing
leaching liquor concentration can be seen in Fig. 5. Lead and zinc re-
H2 O ⇔ H+ + OH– (12) covery increases up to 55% and 12% respectively at NaOH concentra-
HCO3– + OH– ⇔ CO32– + H2 O (13) tion of 6.5 M. Beyond this NaOH concentration metals recovery is kept
constant. This developed alkaline treatment reduces the solid waste of
the high purity zinc oxide production process to 56 kg/t of fed Waelz
- Secondary reactions in the liquor:
oxide with the following composition (Table 6):
Zn2 + + OH– ⇔ ZnOH+ (14) Under high alkaline leaching conditions, lead will form soluble
complexes with OH− and will remain in solution. In aqueous solution,
Zn2 + + 3OH− ⇔ Zn(OH)3− (15)
lead hydroxyl complex ions of Pb(OH)3−, Pb(OH)42 −, PbOH+,
Zn2 + + 4OH− ⇔ Zn(OH)4 –2 (16) Pb2(OH)3 +, Pb4(OH)44 +, Pb6(OH)84 + and Pb(OH)4+ at the pH value
over 12,0 are really stable (Wang et al., 2009). Hence, the quantity of
Zn NH32 + ⇔ Zn2 + + NH3 (17) final solid residue was reduced, recovering suitable metals, and the
2+ remaining solid waste was inertized with this high alkaline washing.
Zn (NH3 )2 ⇔ Zn2 + + 2NH3 (18)
Consequently, it is increased the environmental sustainability of the
Zn (NH3 )32 + ⇔ Zn2 + + 3NH3 (19) industrial plant.
According to the obtained results it can be concluded that the op-
Zn (NH3 )4 2 + ⇔ Zn2 + + 4NH3 (20) timal NaOH concentration to extract the maximum possible metals
quantity from solid residues is 6.5 M (Fig. 5). Then, the caustic soda
- Induced precipitation reactions: solution/exhausted liquor mix ratio by volume was optimized, in order
Zn2 + + CO32 + ⇔ ZnCO3 (↓) (21) to maintain the pH over 11.5, in the following proportion:

1 Volume of exhausted liquor

Zn2 + + 2 OH– ⇔ Zn(OH)2 (↓) (22)
+ ½ Volume of solid waste leaching liquor (6.5 M NaOH)
When the pH is increased above 11.5, two major factors affect the

Table 4
Chemical composition of the liquid waste.

pH [Zn] (g/L) [Pb] (mg/L) [Cd] (mg/L) [Fe] (mg/L) [Cl] (g/L) [F] (mg/L) [NH3] (g/L) [CO2 comb] (g/L)

8.05 6.7–7.1 4.5–5 1–1.5 1.5–2 1–1.5 10–15 43–45 70–72

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N. Antuñano et al. Hydrometallurgy 173 (2017) 250–257

Fig. 4. Proposed flow sheet for the high-purity zinc oxide

production process with the improvement of the solids and
liquids wastes treatment step.

Table 6
Table 5 Chemical composition of the inertized solid residue.
Thermodynamic equilibrium data for chemical reactions.
Element Zn Fe Pb Cd
Chemical reaction Equilibrium constant
Composition (%) 34–36 10–14 21–23 0.1–0.25
NaOH⇔ Na+ + OH− Kb =
[Na +][OH −]
= 6.31·10− 1 a
[NaOH]
NH 4+ + OH– ⇔ NH3 + H2 O Kb =
[NH4 +][OH −]
= 1.77·10− 5 a
[NH3]
– − − 14 a
H + OH ⇔H2O
+ +
Kw = [H ][OH ] = 1.0·10
HCO3– + OH– ⇔ CO32– + H2 O Kb2 =
[HCO3 −][OH −]
= 4.69·10− 11 a
[CO3 − −]
–
Zn 2+
+ OH ⇔ZnOH +
Ke =
[ZnOH +]
= 2.5·104 b
[Zn + +][OH −]
Zn2 + + 3OH− ⇔ Zn(OH)3− β1 =
[Zn(OH)3 −]
= 3.0·10 15 b
[Zn + +][OH −] 3
Zn2 + + 4OH− ⇔ Zn(OH)4−2 β2 =
[Zn(OH)4 − −]
= 3.7·1015 b
[Zn + +][OH −] 4
Zn2 + + NH3 ⇔ Zn NH3 2+
Ke =
[ZnNH3 + +]
= 2.5·102 b
[Zn + +][NH3]
Zn2 + + 2NH3 ⇔ Zn (NH3)2 2+
β1 =
[Zn(NH3)2 + +]
= 6.25·104 b
[Zn + +][NH3]2
Zn2 + + 3NH3 ⇔ Zn (NH3)3 2+
β2 =
[Zn(NH3)3 + +]
= 1.97·10 7 b
[Zn + +][NH3]3
Zn2 + + 4NH3 ⇔ Zn (NH3)4 2 + β3 =
[Zn(NH3)4 + +]
= 2.48·109 b
[Zn + +][NH3]4
Zn2 + 2+
+ CO3 ⇔ ZnCO3 Kps = 2+
[Zn ][CO32 +] = 1.0·10− 10 a

Zn2 + + 2 OH–⇔Zn(OH)2 Kps = [Zn 2+

][OH ] = 1.0·10− 15
− 2 a

a
Martell et al., 1982. Fig. 6. Ammonia and zinc recovery as function of temperature, injecting 60 NL/min of air
b
Sillén et al., 1964. during 120 min.

Fig. 7. Ammonia and zinc recovery as function of used air flow rate at 60 °C during
Fig. 5. pH, lead and zinc recovery as function of NaOH concentration in the liquor. 120 min.

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N. Antuñano et al. Hydrometallurgy 173 (2017) 250–257

Table 9
Identified phases in the XRD pattern of the zinc concentrate by-product.

Ref. code Compound Displacement Scale Chemical formula

name [°2Th.] factor

01-089- Magnesium − 0.105 0.882 (Mg0.06 Ca0.94)(CO3)

1306 calcite
01-079- Quartz 0.015 0.106 SiO2
1906
01-072- Hydrozincite 0.245 0.342 Zn5(OH)6(CO3)2
1100

Fig. 8. Time evolution of the ammonia and the zinc recovery at 60 °C with 30 NL/min of
air flow.

Table 7
Chemical composition of the treated liquor.

pH [Zn] (mg/L) [Pb] [Cd] [Fe] [Cl] [F] [NH3] [CO2

(mg/ (mg/ (mg/ (g/ (mg/ (mg/L) comb]
L) L) L) L) L) (g/L)

9.90 500–600 18–22 >1 10–12 1–2 2–5 280–320 76–78

A combined solution with this mixing ratio must be fed to the am-
monia stripping reactor, which is going to be optimized in the next
experiments. When the pH of the exhausted liquor was increased above
11.5, other operation conditions of the ammonia stripping reactor have
to be defined in order to optimize the liquid waste treatment stage. The
Fig. 9. XRD pattern of zinc concentrate by-product.
stripping ratio (S) characterizes the difficulty of removing the con-
taminant from the liquid phase and it was maximized, optimizing the
variables which influence it: reformulate the fresh liquor (aqueous solutions of ammonium carbo-
nate and liquid ammonia) by simultaneous CO2 capture from Waelz
S = (G
′ (L t))·Hc

where G′/(L/t) = volumetric air-to-liquor ratio; G′ = injected air flow;

L = liquor volume; t = batch cycle time and Hc = Henry's constant
(14)
(temperature-dependent).
The experimental work to study the influence of these conditions
was carried out in a stirred tank using 1,8 l of the combined solution.
This liquor volume supposes 0.0017 m3 of diffusion volume and
0.0114 m2 of diffusion cross-section for the geometry of the used re-
actor with a 4 mm diameter gas injector.
The optimal temperature of the ammonia recovery process was
fixed at 60 °C as it can be observed in Fig. 6. This minimum temperature
is necessary for reaching the maximum ammonia recovery in this step
(Fig. 6). On the other hand, as it is represented in Fig. 7, 30 NL/min is
the optimal air flow in order to obtain the target objective (ammonia
recovery higher than 98%) of the process in the used absorber reactor
(geometry of the designed absorption system).
The optimal ammonia recovery yield at the studied conditions is
98.4% and the zinc recovery yield is 86.3%, when the optimal time to
complete the process is 100 min (Fig. 8). In the liquid waste treatment
stage (under optimized conditions) ammonia gas stream and a pre-
cipitated solid by-product were generated in addition to the treated
liquor. The recovered ammonia can be absorbed in water, in order to
furnace flue gas (Wylock et al., 2014). At the same time, atmospheric
emissions of the plant and the reagents costs are reduced.
The composition of the liquid waste after the developed process is
shown in Table 7.
The precipitated by-product, characterized in Tables 8, 9 and Fig. 9,
is a zinc concentrate which fulfils the specifications (low halogens and
metallic impurities contents) to feed an electrolytic zinc production
process (Guozhu et al., 1999) in alkaline medium (Goodarzi et al.,
2009; Neng Ping et al., 1983; Gürmen et al., 2003; Qiang et al., 2013).
Even if the electrolytic production in acid media is preferred (higher
metallic yield), high carbonates content of this by-product makes more
profitable the alkaline process to avoid the acid spent in the leaching
stage. 88 kg of this by-product per ton of fed Waelz oxide are produced
when the solid and liquid wastes treatment is integrated in the high
purity zinc oxide production process.
Once the precipitated by-product is separated, the remaining solu-
tion must be treated through a simple Fenton Process in order to
achieve environmental legislation limits (pH, ammonia concentration,
chlorides concentration, and so on) before final discharge (De Brito
et al., 2010; Collivignarelli et al., 2017; Benatti et al., 2012). There are
also other alternatives that can be considered. A crystallization (via
water evaporation or via carbonation, injecting CO2 from the zinc

Table 8
Chemical composition of the solid by-product.

Element Zn Pb Fe Cl F Na Carbonates

Composition (%) 30–34 1.5–3 0.1–0.5 0.4–0.6 0.002–0.003 4–6 28–30

256
N. Antuñano et al.
carbonate species calcination stage), will generate an impure Na2CO3
with possible application, for example, as slag forming agent (Me-
tallurgy of lead) or as neutralizing agent of flue gas for several in-
dustrial processes. But the vapour generated need to be treated due to
the ammonia content and this process could be too expensive because
of the low economic value of the obtained product. Another simpler
alternative would be to recycle it into any step of the hydro-
metallurgical liquor regeneration stage. In this case the carbonates
balance must be carefully considered in the design of the absorption
processes.
4. Conclusions
A solid and liquid wastes treatment process has been developed to
be integrated in the hydrometallurgical production of high-grade ZnO
from Waelz Oxide. The process combines the treatment of the solid
residues (from the leaching, oxidation and cementation stages of the
ZnO fabrication) with the liquid waste treatment. This reduces the
OPEX of the integrated plant, increasing the utilization of hazardous
waste through its partial recycle to the same or other processes. It also
reduces the environmental impact through a decrease of the solid and
liquid wastes while they are inertized. In this case, the designed and
optimized process reduces the solid waste by 54.8% (from 124 kg/t of
fed Waelz oxide to 56 kg of inert residue) and inertizes them to facil-
itate their disposal in landfills. Besides that > 5% of initial zinc is also
recovered as a marketable by-product (zinc concentrate) from the solid
residue and the exhausted liquor, reaching a zinc recovery of 94% of
the zinc contained in the Waelz oxide in the integrated process.
Furthermore, 98.4% of the ammonia is removed from the exhausted
liquor, which supposes 38.6% of the total ammonia content needed in
the leaching stage of the optimized high-purity zinc oxide hydro-
metallurgical production process. This ammonia is eliminated from the
liquid waste as ammonia gas stream but it can be used in an absorber to
regenerate leaching liquors, decreasing the ammonia make up re-
quirement of the ZnO hydrometallurgical process. Specifically, the de-
veloped production process, with the improved solid and liquid waste
treatment, makes recoverable the 78.3% of ammonia to prepare the
leaching liquor used in the first stage of the whole process.
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