VOL.

4 (25) JULY / AUGUST 2015 * SUSTAINABLE DEVELOPMENT

NON-FERROUS METALS WASTE AS METALS' RESOURCE.
PART 2 - TECHNOLOGIES FOR METALS EXTRACTION
PANAYOTOVA Marinela
marichim@mgu.bg
Department of Chemistry,
University of Mining and Geology,
Student Town, Sofia 1700, Bulgaria
PANAYOTOV Vladko
vlad_tod@abv.bg
Department of Mineral Processing,
University of Mining and Geology,
Student Town, Sofia 1700, Bulgaria
Summary. This work is aimed to contribute to changing the classical perception for waste from nonferrous metals extraction from a real waste to a resource; to promote transfer of BAT and to encourage the
development of new technologies for slag and residues treatment aimed at recovering valuable metals. The final
goal is to decrease metals content in slag, decrease the mining of raw ores, and to ensure metals needed for the
sustainable development of the society at diminished negative impact on the environment.
Key words: non-ferrous metals slag, copper slag, lead slag, zinc slag, zinc leaching residue

Introduction. Non-ferrous metals slag and

leaching residues occupy large land areas for
their discarding. Usually they bear heavy
metals and iron (Fe), which can be leached,
thus
posing
environmental
problems.
Extraction of heavy metals from the primary
slag is often economically justified, since their
content in the waste is comparable, even
sometimes higher than in the ores, mined out
nowadays (as it has been represented in the
first part of the paper). In addition,
environmental hazard will be diminished, the
left material (iron silicate phase in the case of
slag treatment) is made more acceptable for a
range of commercial applications. Different
technologies for slag (residuals) treatment and
metals recovery have been proposed and are
being developed, such as beneficiation
(crushing and grinding, followed by magnetic
separation,
flotation),
pyrometallurgical,
hydrometallurgical
processes
or
their
combination. The present paper briefly
presents and discusses technologies for
treating slag from copper, lead and zinc
pyrometallurgy, as well as zinc leaching
residue from zinc hydrometallurgy.
Copper
(Cu)
slag.
Beneficiation
technologies. Since, the slag is composed
mainly by iron oxides and silica, a good
response to gravimetric and magnetic
treatment is expected. By passing through

95

several kinds of units for gravimetric

separation, finally heavy and light fractions of
solids can be obtained. The light fraction,
containing mainly silica, could be recycled to
the copper smelting as flux, and the heavy
fraction is treated in a magnetic concentrator
thus obtaining two fractions: magnetic iron
oxide for iron pellet production and non
magnetic fraction for leaching process. Copper
concentrate by using flotation techniques
could be obtained from the latter. The
technique is suitable for small enterprises
because it is simple and effective way to
recover Cu. The slag flotation has become less
important recently due to the decreasing of
copper content in final slags [1].
Slag minerals processing is not suitable for
treating slag containing nickel (Ni), cobalt
(Co) and zinc (Zn), because these metals
generally are entering the Cu concentrate or
tailings [2].
Pyrometallurgical
technologies.
Slag
cleaning/ copper extraction by coal reduction
is a mature technology. In the furnace for slag
cleaning pulverized coal is injected, the
temperature is maintained by means of
oxygen-fuel burners. The coal reduces the
content of magnetite in the bath, decreasing
slag viscosity, and Cu particles are released
forming a rich copper matte (70% Cu) that is
returned to the Cu converter [1]. In another

VOL. 4 (25) JULY / AUGUST 2015 * SUSTAINABLE DEVELOPMENT

application waste Cu slag is mixed generally
with various fluxes such as alumina, calcium
oxide, magnesium oxide, silica as a slag
composition regulator, and carbon as a
reducing agent, and the mixture is melted at a
high temperature (14001500 oC), thereby
separating and recovering iron as an alloy
from the waste slag [3].
The Ausmelt top-submerged lancing
process (a single Ausmelt furnace using a
multistage process) for recovering of Cu, Ni
and Co from smelting and converting Cu slags
has been implemented by Rio Tinto,
Zimbabwe and Anglo American Corporation
[4].
Most often the pyrometallurgical treatment
of copper slag is carried out in electrical
furnaces. In this type of furnace oxides are
reduced by the graphite electrodes and
supplementary coke addition [1].
By processing slags in electrical furnaces
98% recovery of Cu and 96% recovery of
precious metals was achieved in Russia [5].
Mintek Company has developed a
technology for recovering Co, Ni and Cu from
a different non-ferrous metals smelting slag.
The treatment works parallel to the normal
smelting operation, using DC-arc electrical
furnace [6].
Reduction smelting (under N2 atmosphere)
and addition of activated carbon (as reducing
agent) to the slag, and CaO or TiO2 as
modifier was applied to recover cobalt as
cobalt-bearing alloy from converter slag from
Chambishi Copper Smelter in Zambia. Under
the optimum conditions 94.02% Co, 95.76%
Cu and less than 18% Fe in the converter slag
were recovered in a cobalt-bearing alloy, with
the main composition, in %: 1.76-Co, 75.20Cu, 12.85-Fe [7].
Hydrometallurgical technologies. Slag
containing worth to recover quantities of
molybdenum (Mo) and with appreciable
solubility in sulphuric acid (H2SO4) solution
can be leached with addition of iron (III) ions
or hydrogen peroxide (H2O2). After leaching,
solvent extraction and ion exchange can be
applied to separate the dissolved metals,
followed by Cu electro-winning and Mo
precipitation [1].

96

Leaching with H2SO4 under H2O2 was used

to avoid formation of silica gel which hinders
pulp filtration and leads to crud formation
during solvent extraction. In addition,
simultaneous iron (Fe) oxidation and removal
was achieved at treating a Cu smelter slag
from Lubumbashi, Democratic Republic of
Congo. Solutions containing Cu, Co and Zn
were produced, and the metals were extracted
using kerosene Shellsol D70 as diluent.
Copper was extracted with LIX 984 and
stripped with H2SO4 solution. Thereafter, Co
and Zn were collectively extracted with
D2EHPA and then separated by selective
scrubbing with H2SO4 solutions of different
dilutions. An overall recovery of 80% Cu,
90% Co and 90% Zn was achieved in
separated solutions which could be further
treated by electro-winning [8].
Slag of the Balkhash copper plant
(Kazakhstan) was treated in the following
way: The mixture of the slag and ammonium
chloride (NH4Cl), at wt. ratio 1:2, was treated
at 320 C for 120 min and then subjected to
water leaching. After separation the solid
residue was treated with NH4Cl (wt ratio 1:2)
for 160 min, followed by water leaching, then
- solid/liquid separation and Fe(OH)3
production from the liquid phase by addition
of NH4OH. The recovery of Zn, Cu, and Fe
into solution from the first water leaching was,
respectively 91.5, 89.7, and 88.3%. By adding
an ammonia water to the solution hydroxides
of Zn, Cu, Fe, calcium (Ca) and magnesium
(Mg) were selectively precipitated at different
pH values. The NH4Cl was recovered by
evaporation [9].
Leaching with sulfuric acid and sodium
chlorate oxidant and neutralization with
calcium hydroxide was proposed to recover
Co, Zn and Cu (98%, 97%, and 89%
respectively), from Cu smelter slag at
atmospheric pressure, at only 3.2% and 0.02%,
extraction of silicon and iron respectively [10].
Acid roasting of slags followed by hot
water leaching was carried out to bring the Cu,
Co, and Zn from Cu smelter slags into
solution. Totally 88% of Cu, 87% of Co, 93%
of Zn were extracted at optimum conditions.
Application of thermal decomposition prior to
leaching gave small decreases in metal

VOL. 4 (25) JULY / AUGUST 2015 * SUSTAINABLE DEVELOPMENT

extractions, but since less Fe was extracted, it
was favored from the viewpoint of metal
recoveries from the leachates due to the
elimination of the Fe removal step [2].
Bioleaching
technologies.
Chemical
leaching is economic only when recoverable
metals are present at relatively high levels.
Acid bioleaching of metals from final smelter
slag was tested in a continuously stirred tank
reactor (CSTR). The yields of metal
solubilization after 29 days of contact were
41% Fe, 62% Cu, 35% Zn and 44% Ni. Metals
were precipitated in a separate CSTR by
adding to the leach liquors sulfide-rich effluent
from a sulfate-reducing fluidized-bed reactor
(FBR) to desired pH values. Over 98% of the
Cu precipitated at pH=2.8 and over 99% of the
Zn precipitated at pH=3.9. The precipitation of
Ni and Fe required higher pH values and was
less efficient [11].
Mixed technologies. Copper and magnetite
phase were recovered from Daye copper
converter slag by applying the hightemperature modifying method - oxidation
with air. Most of the Cu was deposited at the
bottom of modified slag as a metallic Cu
block. The left material was subjected to
gravity and two stage magnetic separation.
The Fe concentrate of 60.19% () Fe at 90%
recovery rate and Cu concentrate of 92.97%
() Cu at 62.32% recovery rate were obtained
[12].
A process for treatment of ancient copper
smelting slag has been proposed. Copper and
Co are recovered in metallic form and / or as
compounds, whereas Fe is recovered as
magnetic oxide. The process stages include
carbothermal reduction in a DC arc furnace,
granulation, leaching, chemical precipitation,
selective
sulfidizing
roasting,
product
preparations [13].
Recovery of Fe from the waste Cu slag was
achieved by a process including crushing the
slag, reduction reaction at 1250 C, crushing
of the resulting material again to 75104 m,
followed by dry magnetic separation. A
magnetic product containing > 65 wt. % Fe
was obtained from magnetic separation at Fe
recovery > 85% [14].
CuCoFe matte obtained from copper
converter slag by reductive-sulfidizing

97

smelting was crushed, wet ground and then

magnetic separated to produce magnetically
susceptible concentrate (mainly CoFe alloy).
95.75% of Co was recovered by magnetic
separation and 87.8% of Cu and 44.39% of Fe
were left in the tailings. The concentrate was
leached by H2SO4. Under the optimum
conditions 99.81% of Co in concentrate was
selectively leached into the solution, while the
99.86% of Cu remained in residue. The
tailings, containing mainly bornite and
chalcocite, and the leaching residue,
containing mainly metal Cu, were treated by
ore proportioning with Cu concentrate and fed
to the copper smelting furnace [15].
Lead (Pb) and lead-zinc (Pb-Zn) slag.
Lead and Pb-Zn blast-furnace slag often
contains sufficient Zn to make its recovery
profitable. Main processes of the lead-zinc
slag processing by using pyrometallurgical
route are: fuming, Waelz, and electrothermic
process [16]. In the fuming process zinc oxide
(ZnO) in the slag is reduced (usually carbon C and carbon monoxide - CO are applied as
reducing agents) under pressure and at
temperature 1200-1300 C to metallic Zn
(vapor), oxidized by secondary air, and carried
out in the furnace gases for recovery of ZnO
dust. Fuming process (2 to 3 hours) was
chosen to treat lead slag from Trepa
Complex. It is realized through the blowing of
the smelted slag with air and mixing with
reducing agents under pressure. The metal
oxides are reduced and vaporized. The
following reactions take place:
C + O2 = CO2
CO2 + C = 2CO
ZnO + C = Zn + CO
ZnO + CO = Zn + CO2
PbO + CO = Pb + CO2 .
Zinc oxide formed during the oxidation as
powder is taken out along with the gases of the
process. Most of Pb and Cd (if available) are
extracted in a few minutes. The obtained
product (sublimation) contains Zn - 59.9 %
and Pb - 10.53 % [16].
In the Enviroplas process (developed by
Mintek) the liquid slag from a lead blast
furnace is fed to a DC arc furnace, often
together with old dry and granulated slag
(stockpiled in dumps). Metallurgical coke is

VOL. 4 (25) JULY / AUGUST 2015 * SUSTAINABLE DEVELOPMENT

employed as the reducing agent. Coals,
charcoal or other carbonaceous materials, with
low moisture and volatiles can also be used as
reducing agents. Zinc and lead compounds
from the molten bath are reduced to metals and
then evaporated. They enter the Pb splash
condenser, where they are condensed. The PbZn solution is then cooled down to separate the
Zn (at about 450 oC). The condenser off-gas
passes through a combustion chamber, and any
metal oxides are captured in a bag house.
Condenser drosses and the fumes are then pretreated before recycling to the fuming stage.
The process is applicable also for treating
neutral leach residues from the zinc industry
[17].
Bioleaching experiments were carried out
in order to leach heavy metals, such as As, Fe,
Cu, Zn, Pb and Mn from a Pb/Zn smelting slag
from a dump site in Hunan Province of China
using indigenous moderate thermophilic
bacteria (mainly affiliated with Bacillus spp.,
Sporosarcina spp. and Pseudomonas spp.)
[18]. Under the optimum conditions about 86
91% of arsenic - As, 9093% of Cu, 9094%
of manganese - Mn and 8187% of Zn from
the slag have been bioleached in 6 days.
Zinc slag and other solid residues from
pyrometallurgy.Pyrometallurgical
technologies. Slag fuming is often applied.
Slag (liquid - directly from the production
process, or solid - old) is charged into the
water-cooled reactor and melted, where
pulverized coal is injected into the slag bath to
recover Pb and Zn and to raise heat from the
process. Cyclone or converter type furnaces
are used to raise the temperature above 1200
C. The metal oxide reduction takes place.
Metals are evaporated. Above the slag bath the
metal vapour is oxidized with tertiary air.
Subsequently, the gas is cooled and the Zn
containing dust is collected in filters and/or
dust precipitators. The cyclone furnace is
operated with oxygen-enriched air but the
converter is operated with substoichiometric
air. Excess heat is produced and it is recovered
in a waste heat boiler and electricity is
generated. Disadvantages of slag fuming are:
large quantities of exhaust gas, complexity of
the offgas treatment, high demand for coal due
to its double application as fuel and reducing

98

agent. In addition, it is impossible to recover

Zn in metallic form, so the produced ZnO has
to be reduced again in a subsequent step [19,
20].
In more advanced Ausmelt or Isasmelt
process, as the "classical" case of slag fuming,
coal is used as reducing agent and solid fuel is
injected into the molten slag, but the injection
is done through a lance.
The studies proved that the combination of
DC arc furnace processing and charging of
carbon bearing material by hollow electrode
technique is a better combination to extract Zn
and Pb from slag. More Zn is won in flue dust
compared to fuming plants, so that the flue
dust can be used directly as a raw material in
hydrometallurgical or pyrometallurgical Zn
production. Lead is won as crude Pb for
refining [19].
In the plasma arc fuming process the
materials are fed into the slag bath of a plasma
arc furnace where the reactions, producing
ZnO, take place. Coke or similar material is
used as the reducing agent. A slag former is
added, if needed, to the feed. The different
metal oxides are reduced according to the
equilibrium determined by slag temperature
and oxygen potential. The slag temperature is
controlled by the plasma power and the slag
composition. Reduced lead and zinc evaporate.
The off-gases are reoxidised by air to produce
ZnO and PbO. The recovery rate of Zn is
about 92% and the ZnO content is about 88%
[20].
Hydrometallurgical technologies.
A
process is proposed to recover Pb, Zn, and Cd
from a Waelz sintering waste (WSW), based
on the dissolution of the WSW in aqueous SO2
solution
and
then
precipitation
of
ZnSO35/2H2O and CdSO33/2H2O by
adjusting the pH of the solution. The fact that
Pb is not dissolved at all but Cd and Zn are
100% dissolved in aqueous SO2 solutions
made the process selective [21].
Indium (In) was recovered from zinc oxide
flue dust with H2SO4 by oxidative pressure
leaching in an autoclave and KMnO4 and H2O2
as oxidants. The atmospheric pressure leaching
experiments were also carried out. It has been
found that the leaching rate of In can be
effectively improved by oxidative pressure

VOL. 4 (25) JULY / AUGUST 2015 * SUSTAINABLE DEVELOPMENT

leaching. Under the optimum conditions, the
leaching rate of In is more than 90%, which is
increased by 13% compared with that of
atmospheric pressure leaching process without
oxidant under the optimum conditions [22].
Mixed technologies. The Zn plant residue,
discarded as a cake from a Waelz kiln
processing zinclead carbonate ores and
containing 11.3% Zn, 24.6% Pb, and 8.3% Fe
was blended with H2SO4 and subjected to a
process comprising roasting, water leaching
(for Zn extraction), and finally NaCl leaching
(for Pb extraction). About 86% Zn and about
89% Pb were recovered at optimum conditions
[23].
A method to recover iron from Zn calcine
was developed. Zinc ferrite (ZnFe2O4) in Zn
calcine was decomposed to ZnO and magnetite
after roasting under a reducing atmosphere (a
mixture of CO and N2) at over 700 C. Then
magnetic separation was used to recover
magnetite from the roasted products.
Preliminary
ultrasonic
treatment
and
mechanical milling increase the Fe recovery
by 20%. The maximum recovery of Fe reached
to 64.2% under optimal conditions [24].
Other metals (In, Ge, Ga) present
sometimes in the concentrates used for Zn and
Pb production. They tend to be concentrated in
the slags, dross, flue-dusts and residues
produced. Recovery processes of those metals
combine several techniques such as leaching,
cementation, solvent extraction, chlorination,
electrowinning and vacuum distillation. These
techniques can be followed by zone refining
and crystal growth techniques to produce ultrapure metals. Often they are commercially
confidential [20].
Zinc leaching residue (ZLR). ZLR are
classified as hazardous wastes because of their
high level of contained heavy metals. That
why they have to be treated to extract metals,
or to be stabilized before land filling.
Beneficiation technologies. Lead was
recovered (as PbSO4) from Zn leach residues
by sulfidization-flotation. The residue was
leached with water before sulfidization to
eliminate its soluble compounds. De-sliming
and cleaning increased the grade of Pb in the
concentrate. Potassium amyl xanthate,
Aeroflot and Aerophine were the reagents used

in the flotation and sodium sulphide - as

sulfidizating reagent (applied at doses 3 times
more than that for the natural pure anglesite)
[25].
Slag from the Waelz processes, used to
treat residues from Zn production processes,
can be treated in a flotation process after the
slag has been crushed. The flotation process
produces Pb concentrate and a Cu-rich portion
which is returned to Pb or a Cu smelter [20].
Pyrometallurgical technologies. The Zn
leach residue can be sent to an ISF or any
other high temperature smelting furnace. Zinc,
lead, silver (Ag) and other valuable metals are
recovered as metals. The leach residue can
also be processed in a Waelz kiln or Zn
fuming furnace may also be used but SO2
absorption is necessary in such a case. Zinc
and lead are recovered as oxides and sulphates,
and the slag may be treated further by flotation
to recover Ag and Cu [20].
Onsan Refinery of Korea Zinc uses a Top
Submerged Lancing Technology (TSL) to
recover the valuable metals in the residue.
About 82% Zn, 92% Pb, 86% Ag and 61% Cu
in the residue can be recovered by the process
[26]. Zinc residue processing in an Ausmelt
furnace involves the smelting of residues with
reductant coal to produce an oxide fume and
slag containing <3% Zn and <1% Pb. Fuel, air
and O2 are injected into the molten bath via a
vertically suspended lance. Feed materials,
reductant coal and fluxes are added through a
feed port in the furnace roof. The feed
decomposes in the bath and Pb and Zn are
reduced and volatise as metallic species. High
recoveries are achieved of Pb and Zn plus
other high value metallis, such as silver (Ag)
and In to the fume product [27].
Two alternative zinc-fuming processes
have been developed: A) Reductive roasting
followed by an oxidative Isasmelt operation.
During the roasting, a mixture of neutral leach
residue, Cu cement, gypsum and dolomite is
heated by burners and is directly reduced with
solid carbon. The reaction product has low
residual Zn, contains metallic Fe and is
referred to as Directly Reduced Iron (DRI). In
order to remove the remaining impurities from
the DRI and transform them into valuable end
products, the hot DRI is fed into an oxidative

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Isasmelt operation. A clean slag, a Cu-rich
matte and a Zn-rich fume are the end products
of the process. B) The second, i.e. the
Submerged plasma zinc fuming process uses
plasma with natural gas (CH4). The gas is
injected into the slag bath. In parallel, a
mixture of leach residue, petroleum coke
(reductant), a small fraction of Cu cement and
fluxes, is fed continuously into the slag bath.
The solid feed dissolves into the molten bath;
blast gases react with the slag and reductant;
Zn and other volatile metals fume off. Above
the bath, the fume is post-combusted with
secondary air, and the resulting off-gases and
solid ZnO particles are removed from the
smelting vessel. The outputs of the process are
a slag phase, a matte phase, ZnO-powder and
off-gas. The off-gas is treated in an
electrostatic precipitator to recover ZnO [28].
A method was developed for decomposing
zinc ferrite (ZnFe2O4) in ZLR to ZnO and
magnetite after reduction roasting using the
mixture of CO and argon (Ar) as reduction
agent. The following reactions take place:
3ZnFe2O4 + CO = 3ZnO + 2Fe3O4 + CO2
ZnFe2O4 + CO = ZnO + 2FeO + CO2.
By applying a weak reducing agent,
generation of ferrous oxide and metallic iron,
which result from traditional roasting
processes using carbon as the reducing agent,
can be avoided. Moreover, this process also
has the advantages of a lower roasting
temperature than the traditional process [29].
Hydrometallurgical technologies. Usually
different inorganic lixiviants are applied:
sulphuric acid, hydrochloric acid, nitric acid,
caustic soda, brine, ammonia, ammonium
carbonate, ammonium chloride. Acidic leach
solutions, caustic soda and brine solution have
been found to be very effective lixiviant for
the leaching of Pb and Zn. The main target of
the hydrometallurgical treatment usually is the
leaching of zinc ferrite, which occurs
efficiently only at high acidity and
temperatures above 90 C. This treatment of
the leach residue implies a counter-current
sequence of steps with increasing acidity
levels and temperature. Slurry from the final
leaching stage is settled and the overflow
solution is treated to remove impurities
counter-currently taken back in former steps.

The solid in the underflow is filtered and

washed on a filter. The filter cake is disposed
of and the filtrate is recycled to the process.
Different flowsheets are used depending on
factors, such as the choice of the iron removal
process and the available integrated impurity
recovery processes. In addition to Zn, other
metals are also dissolved during that leaching
process. Iron is the major impurity and the Fe
is precipitated in three forms: jarosite, goethite
or haematite. In jarosite precipitation ammonia
or another monovalent cation alkaline
compound is used and Zn calcine for
neutralisation. Up to three stages are used
depending on whether Ag-Pb recovery is
undertaken. A single stage process known as
the conversion process is also applied. In
goethite process ZnS is used for pre-reduction,
oxygen for reoxidation and Zn calcine for
neutralisation. In haematite process SO2 or Zn
sulphide are used in pre-reduction and an
autoclave with O2. The haematite process has
not proved to be viable. The jarosite process is
capable of high Zn recoveries, even with
concentrates that contain 10 % Fe. Similar
recoveries with the goethite process rely on a
low Fe content in the calcine fraction (or ZnO)
that is used for the precipitation in the
hydrolysis stage. Zinc recovery yield is
maximised by washing thoroughly the residue.
Other soluble metals may be treated by
precipitation as hydroxides or sulphides [20].
Rusen et al. [30] developed a process of
acid leaching and brine leaching to reclaim Zn
and Pb, respectively. About 71.9% Zn and
98.9% Pb can be recovered.
A hydrometallurgical process for treating
jarosite residue from Zn hydrometallurgy was
proposed for recovering the contained valuable
metal components. The jarosite was sintered at
650 C, the sintered material was leached in
aqueous NH4Cl solution at 105 C, followed
by filtration. The leaching extraction of Zn,
Pb, Cu, Cd and Ag are more than 95%. During
reduction with Zn powder, more than 93% of
Pb, Cu, Ag and Cd can be simultaneously
recovered [31].
A selective leaching of Zn from the hot
filter cake (HFC) from a cobalt-zinc plant
residue by using sodium hydroxide (NaOH)
was conducted. At this, Zn leaves most of the

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impurities such as Co, Mn, Ca etc. largely
unaffected in the residue. Finally, Zn was
recovered as powder from this solution by
alkaline electrolysis. 88.5% of Zn was
selectively leached out in two steps. The high
purity (over 99%) of Zn powders was obtained
after washing the powders [32].
It
has
been
found
that
the
mechanochemical leaching (with intensive
milling in an attritor) selectively enhanced the
leaching of Zn from HFC in alkaline solution.
Zinc recovery of 99.9% was obtained at
optimum conditions [33].
Recovering of lead in the form of anglesite
with alkaline leaching of Zn leaching residue
was investigated. Under the optimum
conditions, the leaching ratio of Pb reached up
to 99.6%. Lead could be effectively separated
from the pregnant leach solution with chemical
precipitation by Na2S and CO2 addition [34].
A study, carried out to optimize the brine
leaching of metals from hydrometallurgical
residue, found that temperature is a crucial
parameter for Cu, In and Zn extraction, with
contribution rates of 62.5%, 48.4% and 48.3%,
respectively. Lead extraction is significantly
affected by pulp density and NaCl
concentration, with contribution rates for Pb of
54.4% and 35.9%, respectively. At the
optimum conditions, the extraction rates from
the residue were Cu 93.6%, In 94.1%, Pb
91.6% and Zn 93.2% [35].
Mixed technologies. A study has been
carried out on application of ZLR as a sulfur
source to sulfidize heavy-metal-containing
neutralization sludge (NS), which could then
be separated by flotation for metal recovery.
NS and ZLR were obtained from the Zhuzhou
Smelter Group, which is one of the largest Zn
and Pb smelter plants in China. A mixture of
NS, ZLR and additional sulfur was first milled
by ball milling, and then successively treated
by hydrothermal sulfidation and flotation. The
sulfidation percentages of Zn and Pb were
82.6% and 95.6%, respectively. The main
sulfidation products were ZnS and PbS.
Flotation tests revealed that Zn and Pb can be
enriched with a concentrate grade of 21.3% Zn
and 3.4% Pb. Toxicity characteristic leaching
procedure results indicated that stabilization of
NS and ZLR occurred after sulfidation [36].

Leaching and recovery of Zn from ZLR,

based on a membrane filter press (MFP), was
studied. The leaching, performed via washing
at 90 - 96 C for 90 min with spent electrolyte
using a MFP, results in a Zn extraction rate of
97%, and almost all of the Zn leached is
recovered after water washing with MFP.
Compared
with
the
traditional
hot
concentrated acid leaching process, the process
based on MFP as a leaching reactor ensures a
high extraction rate at reduced leaching time.
The thickening, pulping, second leaching,
washing, filtering and pressing is integrated
and realized using a single MFP. The Zn
calcines with particle size of less than 106 m
and MFP chambers with a width of 30 mm are
proper for establishing uniform filter cakes to
obtain acceptable leaching and recovery
results [37].
Neutralization sludge. Hydrothermal
sulfidation was employed to sulfidize the
heavy metals in heavy-metal containing sludge
generated in the disposal process of
metallurgical wastewater treated by lime milk
to precipitate heavy metals in Zhuzhou
Smelter Group, China. Sulfur was used as
sulfidizer. Hydrothermal sulfidation shows
advantages over conventional methods,
especially for the sulfidation of heavy metal
containing sludge with very high moisture
content. First, the reaction occurs efficiently
without any pretreatment, such as baking or
grinding. Second, sulfur is a low-cost material
and causes only slight secondary pollution as
compared with other sulfidizers, such as Na2S.
Hydrothermal sulfidation offers a way to
modify the metal sulfide surface and structural
properties in order to improve their
floatability. After the hydrothermal sulfidation,
the sulfidation percentage of Zn and Pb
reached up to 85.0% and 75.4%, respectively.
Flotation test has indicated that 33.3% of Zn,
58.9% of Pb and 68.8% of Cu can be
recovered from the sludge. The lower recovery
of ZnS might be attributed to its crystal grains
which are finely dispersed [38]. Further
studies aimed at improving the flotation
recovery of zinc from the sludge were carried
out. After the hydrothermal sulfidation, the
separated solid material was subjected to
flotation where the following reagents and

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flotation times were applied:
Sodium
hexametaphosphate + CMC - 400+200 g/t, 3
min; CuSO4 - 400 g/t, 3 min; Butyl xanthate +
Diethylditiocarbamate 40 + 40 g/t, 2 min; and
pine camphor oil - 30 g/t, 1 min. At a
precursor concentration of 15%, a Zn/S molar
ratio of 1:1.2, a liquid/solid ratio of 3:1, the
sulfidation extent of Zn in the sludge was
greater than 92%, while the flotation recovery
of Zn reached up to 45.34% [39].
The zinciferous sludge - a sediment from
the wastewater treatment, which contains
metals, such as Zn, Ca, and Fe was subjected
to a H2SO4 selective leaching without any
other addition of
oxidant and at pH
controlling to recover Zn. Hydroxides of
contained metals are formed at different
hydrolysis pH values for Zn2+ and Fe3+ during
the leaching process. The following reactions
take place:
CaCO3(s)+H2SO4(aq) = CaSO4 (slightly soluble)+
H2O+CO2(g)
2Zn2+(aq)+2H2O=2Zn(OH)2(s)+4H+(aq) (pH>5.6)
2Fe3+(aq)+3H2O=2Fe(OH)3(s)+6H+(aq) (pH>1.8)
The leaching rate of Zn and Fe are 91.20%,
1.35% respectively [40].

metals slag, ZLR and neutralization waste:

beneficiation,
pyrometallurgy,
hydrometallurgy,
bioleaching,
their
combination. The most suitable technology
depends on the valuable metals concentration,
chemistry and mineralogy of the technogenic
waste. Generally, beneficiation technologies
alone do not reach desirable results.
Pyrometallurgy is more easily applicable.
However, it needs: operating at high
temperatures, strict temperature control, fresh
fluxes addition, and big amounts of material to
be treated. Hydrometallurgy is applicable to
smaller volumes and technogenic waste with
varying composition. However, the flow
sheets applied are more complicated.
Bioleaching is the most suitable technology for
large amounts of waste bearing valuable
metals in low concentrations. However, the
processes are lengthy. Usually, best results are
obtained by combining two or more types of
technologies. The most suitable one will be
decided on the basis of knowledge on
chemistry and mineralogy of the waste;
thermodynamics and kinetics of the expected
extraction process; combined with laboratory
and pilot tests.

Conclusions. Different technologies are

applicable to extract metals from non-ferrous
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