Journal of Cleaner Production 164 (2017) 534e542

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Journal of Cleaner Production

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

New residue-free processing of copper slag from smelter

Leila Miganei a, Eberhard Gock a, Marcela Achimovi
 a, c, *, Lutz Koch b, Horst Zobel b,
cova
€ rg Ka
Jo €hler a

a
Institute of Mineral and Waste Processing, Waste Disposal and Geomechanics, Clausthal University of Technology, Walther-Nernst Str. 9, Clausthal-
Zellerfeld 38678, Germany
b
Projektservice GbR Eisleben, Wolfero€der Weg 14, Lutherstadt Eisleben D-06295, Germany
c
Institute of Geotechnics, Slovak Academy of Sciences, Watsonova 45, Ko
sice 04001, Slovakia

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

Article history: Deposited copper slag originated from a region Mansfeld (Saxony-Anhalt, Germany) was characterized
Received 27 February 2017 from mineralogical, chemical and structural point of view for purpose of its sustained processing and
Received in revised form removal. Subsequently hydrometallurgical processing of copper slag was investigated because of
23 June 2017
extraction of metals as Zn, Cu, Ni, Co, Mo, Cr, V and Fe in total content about 5%. Although the slags with
Accepted 23 June 2017
their mineralogical composition of calcium, magnesium, aluminum, and iron silicates are perfectly
Available online 27 June 2017
suitable as building materials, their cumulative heavy metal content prevents this. Novel residue-free
recycling process for copper smelter slag was developed which consists of sorting, roasting, leaching
Keywords:
Copper slag
with HCl, carbonate precipitation, precipitate complexation and solvent extraction of metals steps. This
Leaching kinetics process solves the problem with calcium silicate matrix which enclosed dissolved metals. By setting pH
Residue-free processing of leaching process to ~2.5, 80e90% of Cu can be extracted and dissolution of silicate matrix can be
Mass balance prevented. Mass balance of process strategy indicates the proceeds from four marketable products:
Products characterization blasting agent, cement additive, metal salts solution, and fertilizer, which make the process more
economical with sustainable benefits. Economic evaluation of new process is also done and confirmed its
utility and favourable balance.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction concentrations of Pb(<200 ppb), Ni(<50 ppb) and Cd(<30 ppb) are
under allowed value (<1000 ppb) according to the technical in-
Based on the research conducted on the possible application and structions for municipal waste (TA-Kl.I). This research has shown
utilization for the copper slag incurred worldwide, the setting-up of important economic and environmental advantages due to utili-
Database of Mansfelds copper slag was initiated and featured its zation of the waste products, copper slag and fly ash for production
diverse profile (Zobel, 2016). of cement material along with the heavy metals immobilization
The interesting investigation of the using of copper slag (14.4%) through the synthetic storage material formation. Moreover, this
together with WIP-fly ash from waste incineration plants (50.4%) method of the processing of the industrial wastes, which are
and limestone powder (35.2%) for the production of alinite cement contaminated with heavy metals, could be allowed for their daily
(62.3% CaO, 23.1% SiO2, 3.3% MgO, 7.6% CaCl2, 4.7% Al2O3) and for disposal.
the immobilization of heavy metals through the formation of The partial substitution of silica sand for the production of
synthetic storage minerals, especially Cl-ellestadite (Ca10[(SiO4)3(- concrete and mortar by copper slag can enhance their properties.
SO4)3Cl2]) by thermal treatment at 900
C for 60 min have been The reduction of the hygroscopicity of concrete mixed with copper
performed (Tewelde, 2004). The elution examinations of the alinite slag, and the increase in the strength, if the share of copper slag
and Cl-ellestadite mixture have shown that the values of eluate does not exceed <80%, are highlighted (Murari et al., 2015). It has
been referred that NaOH-activated copper slags mortars have bet-
ter corrosion resistance than Portland cement mortars (Shi and
* Corresponding author. Institute of Mineral and Waste Processing, Waste Qian, 2000). According to new technological method which uti-
Disposal and Geomechanics, Clausthal University of Technology, Walther-Nernst lizes the copper slag for self-compacting concrete, the durability
Str. 9, Clausthal-Zellerfeld 38678, Germany. and longevity of structural design of concrete can be improved
E-mail address: [email protected] (M. Achimovi
).
cova

http://dx.doi.org/10.1016/j.jclepro.2017.06.209
0959-6526/© 2017 Elsevier Ltd. All rights reserved.
 L. Miganei et al. / Journal of Cleaner Production 164 (2017) 534e542 535

(Fadaee et al., 2015). Using of copper slag for the improvement of

the physical and mechanical properties in the construction, main-
tenance and restoration of the roads has been also reported
(Behnood et al., 2015). In a study carried out by Biswas and Sata-
pathy copper slag was used as a filler in the glass epoxy compounds
which showed the increase in the tensile modulus, bending, shear
and impact strength (Biswas and Satapathy, 2010). Apart from
volcanic basalt, copper slag is commonly added and spun into heat
insulation panels. An already well-established application of cop-
per slag with grain fractions between 0.2 and 2 mm is its use as an
abrasive blasting agent for the treatment of metal surfaces, rust
removal, dental work, as well as synthetic and precision casting
products.
Many potential fields of application for copper slag apart from
blasting agents are currently not being exploited because of the
Fig. 1. Dumping of copper slag from the shaft furnace at the Helbra primary smelter,
metal content, for which so far no economic regulation is in place
Saxony-Anhalt, Germany.
regarding its extraction. For economic reasons, oxidizing sulfuric
acid pressure leaching is not an alternative if the metal contents in
the copper slag are following <4% Cu, <0.5% Co and <2% Ni (Anand 2.7%, the total metal content is around 5%. Very low contents of the
et al., 1983). With open sulfuric acid leaching using Fe3þ ions as an rare earth metals Ce (57 ppm), La (25 ppm), and Nd (29 ppm) are
oxidant, the complete extraction of Cu takes 24 h (Aydogan et al., also worth mentioning.
2000). The X-ray diffraction analysis has shown the glassy or vitreous
An interesting processing proposal was developed for the type of slag as being X-ray amorphous. For the crystalline type of
recycling of copper slag from the copper production in Lubumbashi slag, the following phases were determined diopside Ca(Mg,Al)(-
(Congo) with a total amount of 14 M t (Banza Numbi, 2000). Si,Al)2O6 (JCPDS PDF 025-0154), (Zn,Cu,Si)S (JCPDS PDF 014-0542)
Through the combination of sulfuric acid digestion of un-milled and quartz SiO2 (JCPDS PDF 016-0380) (see Fig. 2).
copper slag (grain size distribution 100% < 10 mm with 1.35% Cu, The optical microscopy study of crystalline copper slag has
0.86% Co, 12.53% Zn, 100 ppm Ge) and subsequent roasting at shown the calcium silicate matrix, in which the metals or metal
600
C, the oxidized metals can be leached with water. During the sulfides are enclosed in the form of droplets (see Fig. 3). (Miganei
roasting process, sulfur is added as a combustible. With the help of et al., 2016).
an internal cycle, all the SO2 exhaust fumes are converted into According to reference the hydrometallurgical processing via
H2SO4 using the lead chamber process. The recoveries were 95% Cu, leaching with sulfuric acid, ammonia and salt solutions always
90% Co, and 90% Zn. The reprocessing of the sulfate solutions was requires cost intensive fine grinding. During the leaching of sili-
done via solvent extraction. The balancing of the mass flow of the ceous copper slags with sulfuric acid, amorphous SiO2 is converted
processes shows, that per 1 t of slag material, there was a residue of into silica gel (H2SiO4, which also absorbs solved valuable metals
925 kg, neutralization of the sludge from the wastewater treatment and complicates the filtration of the leaching residues (Sigg and
is also needed. Recycling of the residues was not planned; they are Stumm, 1994).
deposited in a tailings pond, which are in contradiction with
environment.
This work deals with a novel residue-free recycling technology 2.2. Comminution, leaching and crystallization procedure
for purpose of the deposited copper slag sustained processing and
removal whereby its environmental impact can be reduced. For the laboratory investigations, 1 t of slag was subjected to
Ammonia solution, sulfuric acid and hydrochloric acid for dissolu- pre- and medium comminution using impact crushing. Impact
tion of the metals from slag have been tested. The leaching kinetics crushing is known for its selective comminution effect. While the
for Cu, Ca and Si has been investigated and the products of the medium work index Wim of the vitreous structure is in the
developed technology as a sustainable benefit have been chemi- magnitude of basalt around 19 kWh.t1, the work index Wim of the
cally and structurally characterized and economically estimated. crystalline structure is estimated to be in the magnitude of quartz
around 15 kWh.t1. According to Bond (1954), Wim represents the
2. Material and methods total work needed for the comminution of a mass unit of material of
“endless” grain size to 80% < 100 mm, which is done by a commi-
2.1. Slag characterization nution machine, in this case a Bond mill (Schubert, 1998). The mass
ratio of vitreous slag: crystalline slag after comminution and
Copper slag (Mansfeld, Germany) from shaft furnace is dumped sieving was 1:3.
and cooled in periodic intervals, which generally generates two Ammonia solution, sulfuric acid, and hydrochloric acid leaching
types of structure in the slag material (Fig. 1). The parts in contact of crystalline copper slag have been tested for selective metal
with the surrounding air form quickly solidifying mineral glass extraction. A volume of 500 mL 20% aqueous ammonia solution and
while the layers underneath form crystalline structures due to the 50 g of slag were mixed in leaching vessel making 100 g.L1 slurry
slow cooling rate. In terms of the chemical composition, especially density, agitated and heated to 40
C. The leaching was performed
the metal contents, these two types of slag are identical (Table 1) for 60 min and the aliquots (10 mL) of the solution were withdrawn
(Miganei et al., 2016). at appropriate time intervals 5, 15, 30 and 60 min for determination
Apart from sulfur, which can be attributed to the sulfide resi- of the contents of the dissolved elements by inductively coupled
dues, 0.23% of carbon from the shaft furnace operation is also plasma spectroscopy (ICP-OES Vista MPX, Varian). For sulfuric acid
detectable. In terms of recycling, Zn (1.2%), Cu (0.23%), Ni (118 ppm), leaching dilute 5% H2SO4 and temperature 70
C were applied. For
Co (134 ppm), Mo (322 ppm), Ce (57 ppm), V (0.16%) and Pb hydrochloric acid leaching concentrated 37% HCl, temperature
(805 ppm) are taken into consideration; including the Fe content of 70
C, slurry density 100 g.L1 and 1 t of slag per 1 t of HCl were
536 L. Miganei et al. / Journal of Cleaner Production 164 (2017) 534e542

Table 1
Chemical composition of glassy and crystalline copper slag.

Elements (wt.%) Al C Ca Cu Fe K Mg Mn Na P S Si Ti V Zn
7.27 0.23 15.08 0.23 2.69 2.98 3.00 0.26 2.15 0.10 0.26 22.02 0.42 0.16 1.21
Elements (ppm) As Ba Co Cr Mo Ni Pb Sr Y
102 428 134 264 322 118 805 294 33
Rare earth elements (ppm) Ce Dy Er Eu Gd Ho La Lu Nd Pr Sm Tb Tm Yb
57 <5 <5 <5 <10 <5 25 <5 29 <5 <5 <5 <5 <5
Radioactive elements (ppm) Th U
<25 <200

Fig. 2. X-ray diffraction patterns of crystalline and vitreous type of copper slag. D-diopside Ca(Mg,Al)(Si,Al)2O6, S-(Zn,Cu,Si)S, Q-quartz SiO2.

step the melting was ashed in a muffle furnace at 600
C for 2 h in

order to obtain a solid crystalline product.

3. Results and discussion

3.1. Kinetics of leaching

The advantages of ammonia leaching are that Ca, Si, and Fe do

not dissolve. It was attempted to digest the metal content of slag by
means of its fine grinding <10 mm. This method, however, proved to
be unsuitable due to the high metal losses attributed to the sulfide
compound in the case of copper. Sulfuric acid leaching inevitably
leads to a conversion of Ca into gypsum. If the suspension density is
kept at 100 g.L1, Si will only partially dissolve. Due to aging and
exceeding the solubility product, silica gel will precipitate, which
will cause an increase in volume by the factor 5 as well as metal
absorption. If the leaching process is done using an increased initial
acid concentration, an intermediary dissolution of silicates is
Fig. 3. Ore microscope micro sections of crystalline copper slag type with the inevitable. This goes for sulfuric as well as hydrochloric acid
encapsulated metal drops. leaching. Depending on the conversion the share of free acid de-
creases as the time of leaching increases. In the pH~3, the dissolved
silicates are precipitated again in the form of voluminous silica gel.
used. Leach liquor was precipitated with NH4HCO3 to pH ¼ 7 and
This precipitation product with absorbed dissolved metals requires
after solid/liquid separation the resulting supernatant solution was
a laborious washing process, so that a closed process water cycle is
evaporated by heating at 105
C to become saturated. In the next
impossible to implement. For hydrochloric acid leaching at 70
C
 L. Miganei et al. / Journal of Cleaner Production 164 (2017) 534e542 537

with slurry density 1 t of slag per 1 t of 37% HCl, i.e. with a high solid oxidants. However, since the effective leaching of the metals at
content of raw material a rubber protective lining of 1000 L room temperature assumes a leaching time of more than 4 h, a
leaching vessel must have been used because of the corrosion leaching temperature of 70
C is required. Under these conditions,
protection reasons, as a chemical resistance and anti-abrasion the oxidation with atmospheric oxygen is not effective due to the
behaviour. low oxygen solubility. The same applies to the use of H2O2 which
Fig. 4 shows the pH dependency of HCl leaching process using quickly decomposes if it is subjected to hot solution and therefore
the main elements of the slag Cu, Si, and Ca as an example. At a needs to be added in disproportionately high amounts. Another
pH < 1, 70% of Cu has dissolved after 15 min of leaching. At the same possible oxidation reaction is the conversion of Cu-sulfide with
time, approx. 40% of Si and 50% of Ca are converted into chlorides. CaO2, which can already be added during the grinding process. As
At pH ¼ 2.5, the solution equilibrium of Si-chloride is reached and expected, oxidation reagents can be substituted, if roasting of the
Si precipitates as strongly voluminous silica gel after 30 min of copper slag continues by passing through the rotary furnace at
leaching. The released HCl leads to the further dissolution of Cu 800
C. Fig. 7 shows the decomposition of copper slag during HCl
with a yield about 90% after 60 min of leaching. With this reaction leaching at different oxidation conditions. In all cases Cu-extraction
mechanism in mind, an important change can be made to the of 80e90% is achieved after 60 min of leaching. Without the oxidant
process management. Cu-extraction is ~1% only.
As shown in Fig. 5, the leaching was done at pHstat~2.5. By this
way, the required acid can be cut by 50% and the dissolution of the 3.2. Process concept
silicate matrix can be prevented. Therefore, this method allows
selective metal leaching. If using an increased initial acid concen- Based on the described results a concept of the overall process of
tration, the Cu extraction is in the same order of magnitude as with copper slag recycling as a patent was registered (Fig. 8) (Gock et al.,
excessive acid. It is also interesting to see that, with this manner, 2016). By means of classifying the copper slag into the vitreous and
the Ca extraction can be reduced. The investigations on the influ- the crystalline type, there are two possibilities of recycling. The
ence of the grain size on the extraction of metals showed that ultra- vitreous type is subjected to a step-by-step crushing with classifiers
fine grinding to <10 mm is not necessary for digestion. According to for the production of blasting material. The usage of the vitreous
the presented investigations, a grain size of 100% < 2 mm is suffi- structure requires a sophisticated comminution concept; the fine
cient for the hydrometallurgical digestion of copper slag (Miganei grain fraction <0.2 mm must be extracted and added to the cement
et al., 2016). additive process in order to be able to guarantee residue-free slag
Fig. 6 shows the scanning electron microscope (SEM) images of recycling.
the residues after HCl leaching of the slag. A siliceous carbonate For the crystalline type, the crushing machines from the blasting
matrix remains as a crystalline frame after leaching of the metals media production are used, but no specific classifying devices are
and partially Ca as well. The use of this residue as a cement additive required. The crystalline slag material crushed to <2 mm is sub-
offers the advantage of easier grindability in case further grinding is jected to subsequent roasting in a rotary furnace at 800
C in order
desired. This also drastically reduces the costs for comminution to oxidize the sulfidic bound metals, especially Cu. The use of
(Miganei et al., 2016). oxidation reagents during leaching is thus substituted. According to
In general the leaching experiments showed that the metals Ce, reaction-kinetic leaching investigations, selective metal leaching
Zn, Co, Mo, and Ni except for Cu can be leached without the use of with HCl is possible in the pH range ~2.5, and intermediary

Fig. 4. Dependencies of the recoveries of selected slag elements on pH range ¼ 0.3e3, vs. time of HCl leaching.
538 L. Miganei et al. / Journal of Cleaner Production 164 (2017) 534e542

Fig. 5. Dependencies of the recoveries of selected slag elements on pHstat~2.5, vs. time of HCl leaching.

dissolution and precipitation of the silicates due to an excessive

initial acid concentration can be prevented. With the help of
NH4HCO3, partially dissolved Ca is recovered from the metalliferous
chloride solution in the form of CaCO3 as well as Fe and Mn in the
form of hydroxides. This collective precipitation product can be
reunited with the siliceous residue, so that the Si-Ca-Fe ratio of the
original slag remains the same. In the next step, the also precipi-
tated metal carbonates are complexed as metal amines using
NH4OH and stripped as the sulfates after collective and selective
solvent extraction with H2SO4. The pure metal sulfate solutions are
then the raw material for the electrolytic pure metal production
(Gock et al., 2016; Miganei et al., 2016).

3.3. Products of the proposed process

The quality of the obtained products after proposed recycling

process is relevant for the utilization of copper slag. The mass
balance of the developed process strategy in Fig. 8 indicates the
obtaining of the following four products: blasting agent (Product 1),
cement additive (Product 2), metal salts (Product 3), and fertilizer
NH4Cl/MgCl2 (Product 4).
The blasting agent (Product 1) generated during the recycling is
already being manufactured and sold in low numbers. It is a
disposable blasting agent for corrosion protection with grain sizes
from 0.2 to 2 mm. In the proposed coupling of hydrometallurgical
slag recycling and production of blasting agent, there is the chance
to drastically increase the product flows and, therefore, to make the
entire process more economical.
The use of the calcium silicate-the residue of copper slag after
leaching of metals as a cement additive (Product 2) is also partic-
ularly attractive, unlike fine ground slag in its original state which
the mixing ratios are limited by the metal content because of the
metals elution exclusion. Table 2 shows the composition of the
received calcium silicate residue compared to the typical chemical
composition of a Portland cement clinker (Büchel et al., 1999).
Fig. 6. SEM images of the slag leaching residues after leaching.
Compared to Table 2, the leaching residue comes very close to the
 L. Miganei et al. / Journal of Cleaner Production 164 (2017) 534e542 539

Fig. 7. Influence of the oxidants on Cu-extraction from slag using HCl leaching.

composition of Portland cement. Deficiency of CaO can be settled value-maximum value) of Portland cement from the literature
by its supplementary addition to the calcium silicate residue. (Achternbosch et al., 2003). In all cases except for Pb, the values are
Another possible influencing factor of the cement behaviour is the below the maximum heavy metal concentrations. For the assessing
silica modulus, typically equals 2-3. It is derived from the ratio of of environmental impact consistent with European Commission
SiO2 to the sum of Al2O3 and Fe2O3 and determines the setting rate view (Van der Sloot, 2000) the leaching tests of the calcium silicate
of the cement. In our case the calculated silica modulus equals 3. If residue at various pH are needed.
it is too high, the cement is expected to take a long time to set. The The selective treatment of the metal salts or metal electrolytes
ratio Al2O3 to Fe2O3 determines the alumina modulus. If it is < 0.67, (Product 3) is more complicated. One option is to generate collec-
no tricalcium silicate will form in the melt. In our case this ratio is 3 tive metal salt solutions and sell them as semi-finished product.
and it means that the conditions for alumina modulus can be ful- This would save an estimated 30% of the investment cost, which
filled. Another indicative value is the hydraulic modulus. It results occur for the metal recovery by means of solvent extraction.
from the ratio of CaO to the sum of SiO2, Al2O3 and Fe2O3 and should Regarding the necessary residue-free processing of copper slag, the
be between 1.7 and 2.3. In our case hydraulic modulus is 0.23 hence, solvent extraction of metals is a niche for which outsourcing would
CaO must be added. be the most economical solution. In terms of covering the costs for
The properties of Portland cement are determined according to the processing of the copper slag, the refinement of the required
their clinker phases: Ca3SiO5(alite) - fast setting/high stability, chloride content in the form of a special NH4Cl-MgCl2 dual salt
Ca2SiO4(belite) - slow, steady setting/high stability and 3CaO.Al2O3 fertilizer is interesting (Organization and Center, 1979).
- fast setting/sensitive to acidic water. The phases Ca3SiO5 (JCPDS Fig. 10 shows the X-ray diffraction pattern of Product 4 with the
PDF 013-0209), b-Ca2SiO4 (larnite, JCPDS PDF 033-0302) and CaO phases NH4MgCl3.6H2O (JCPDS PDF 025-0039) and MgCl2.2H2O
(JCPDS PDF 037-1497) generated from the calcium silicate residue (JCPDS PDF 003-0765). In Asian countries, NH4Cl mixed with
obtained after leaching of investigated copper slag and after its phosphates and Mg-salts is used for growing rice or cotton (Ashraf
burning at 1400
C for 10 h with the addition of CaO were detected et al., 2005). Rice is sensitive to fertilizers containing nitrates
by X-ray analysis (see Fig. 9). According to reference (Kim and Hong, (Winnacker and Küchler, 2005). It can be assumed that the
2004) in normal Portland cement clinker Ca2SiO4 occurs as a resulting Product 4 is marketable or capable of being the raw ma-
metastable high-temperature b-phase and its stabilization down to terial for a final cleaning step in order to safely eliminate the in-
room temperature could be made by chemical-stabilizing ions e.g. fluence of possible contaminations.
Al3þ,Fe3þ, Kþ, P5þ, S6þ. This stabilizing effect of the ions presented
in investigated calcium silicate residue was probably performed
3.4. Evaluation and estimated favourableness of the proposed
and b-Ca2SiO4 in addition to Ca3SiO5 was formed. The highest
process
concentration of doped Al3þ ions can increase reactivity, i.e. degree
and rate of cement hydration, which should be examined with the
It is obvious that the applied copper slag presents a raw material
additional investigations.
resource, which can be widely utilized. Restrictions imposed by the
The possibility of the leaching residue using as a cement addi-
Radiation Protection Ordinance x28, which up until now prevented
tive has thereby been proven. However, further research and ex-
the utilization of copper slag, were eliminated in January 2016,
periments are needed to evidence its suitability as a cement binder.
since the allowed threshold values for the contamination of people,
Table 3 shows the comparison of the heavy metal concentrations of
goods, and the environment in roadway construction have been
the leached copper slag residue with the range data (minimum
met. The only limitation for the use of copper slag is that it may not
540 L. Miganei et al. / Journal of Cleaner Production 164 (2017) 534e542

Fig. 8. Flowsheet of the copper slag recycling with the mass balance.

Table 2
Comparison of the calcium silicate residue chemical composition with a Portland cement clinker.

Chemical composition (%) SiO2 CaO Al2O3 MgO Fe2O3 K2O/Na2O Mn2O3 SO3 TiO2 P2O5

calcium silicate residue 50.4 15.4 12.2 4.3 4 2.6/0.7 0.5 0.1 0.3 1.5
Portland cement clinker 16e26 58e67 4e8 1e5 2e5 0e1 0e3 0.1e2.5 0e0.5 0e1.5
 L. Miganei et al. / Journal of Cleaner Production 164 (2017) 534e542 541

▫
Fig. 9. X-ray diffraction pattern of the calcium silicate residue after burning with the addition of CaO. C- Ca3SiO5, -b-Ca2SiO4, A-CaO.

Table 3
Comparison of the heavy metal concentrations of calcium silicate residue to Portland cement.

Heavy metal concentration Cd Co Cr Cu Mn Ni Pb Tl Zn

(wt.%)

Calcium silicate residue <0.0005 0.0017 0.01 0.0038 0.07 0.0022 0.0416 <0.0002 0.025
Portland cement 0.000003 0.00003 0.0025 0.0014 0.0107 0.0014 0.0005 0.000002 0.0021
e0.0006 e0.0021 e0.0712 e0.0098 e0.39 e0.0097 e0.0254 e0.00041 e0.0679

▫
Fig. 10. X-ray diffraction pattern of the fertilizer (Product 4) C-NH4MgCl3.6H2O, MgCl2.2H2O.
542 L. Miganei et al. / Journal of Cleaner Production 164 (2017) 534e542

be used for the construction of sports fields and children’s solution and fertilizer which make the process economically
playgrounds. favourable with sustainable benefits. Implementation of the
Partial solutions, such as metal extraction, can be excluded for developed recycling technology could be also decrease the envi-
ecological reasons, since new and larger mass flows would arise ronmental impact of the worldwide deposited copper slags.
from the use of reagents, requiring the depositing of sludgy resi-
dues in tailings ponds with drainage water checks. Furthermore,
small contents of the radioactive elements Th (<25 ppm) and U Acknowledgements
(<200 ppm) occurring in copper slag are dissolved as chlorides in
the leaching step and concentrated mainly in Product 3, whereby We would like to thank the German Federal Ministry for Edu-
for the large volumes strict health standards for radioactive pro- cation and Research (BMBF) FKZ033RK017B for financial support.
tection of the workers and public must be achieved. Therefore, only
those solutions are viable, where all resulting products allow a win-
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metals was proposed and developed. Compared to ammonia Ash, Mansfelds Copper Slag and Limestone. Martin-Luther-University Halle-
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required acid can be cut by 50% and undesired dissolution of silicate
long-term environmental behavior in construction products during service life
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marketable products: blasting agent, cement additive, metal salt Mansfeld, Germany (in german).