HYDROM-04170; No of Pages 9

Hydrometallurgy xxx (2015) xxx–xxx

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Hydrometallurgy

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Recovery of high value copper and zinc oxide powder from waste brass pickle liquor by
solvent extraction
Manish Kumar Sinha a,b, Sushanta Kumar Sahu a,⁎, Swati Pramanik a, Lal Bahadur Prasad b, Banshi Dhar Pandey a
a
Metal Extraction and Forming Division, CSIR-National Metallurgical Laboratory, Jamshedpur 831007, India
b
Department of Chemistry, Banaras Hindu University, Varanasi 221005, India

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

Article history: Solvent extraction of Cu and Zn from spent brass pickle liquor has been carried out using LIX 984N as an
Received 23 May 2015 extractant. Very high difference in ΔpH1/2 value for the two metals during the extraction indicates the ease of
Received in revised form 14 August 2015 separating them under the appropriate conditions. Based on the bench scale results, metals were separated in
Accepted 15 September 2015
a continuous mode using a laboratory scale mixer settler unit from the spent brass pickling solution containing
Available online xxxx
35 kg/m3 Cu, 30 kg/m3 Zn, 1.5 kg/m3 Fe, 0.75 kg/m3 Cr, 0.03 kg/m3 Ni and 70 kg/m3 H2SO4 with 30% LIX 984N
Keywords:
in kerosene. High copper extraction (99.9%) at the phase ratio (O/A) of 2/1 was obtained at the equilibrium pH
LIX 984N of 2.5 in a two-stage counter-current extraction process, leaving behind Zn, Cr and Ni in the raffinate. Zinc
Brass pickle solution from the chromium free solution was then quantitatively extracted in three counter-current extraction stages
Counter-current extraction at pH 5.5 and O/A = 2/1 with negligible co-extraction of nickel. From the respective loaded organic phases,
Hydrothermal synthesis copper and zinc were completely stripped off using 150 kg/m3 H2SO4. The stripped solutions of Cu and Zn
Cu powder were utilized for the synthesis of high pure Cu metal powder and ZnO particles by the hydrothermal
ZnO powder reduction/precipitation processes. Copper powder was synthesised in an autoclave at 20 bar H2 pressure and
423 K in 2 h. On the other hand ZnO powder (4 bar) was prepared from zinc striped solution at pH 12 in an
autoclave under autogenous pressure at 423 K in 2 h. The purity and morphology of the as-prepared powders
were determined by chemical analysis, XRD and SEM-EDS studies.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction
Industrial wastes generated in metallic industries are generally
laden with heavy metals. Brass pickle liquor is also a kind of industrial
waste generated during cleaning of the brass surface which tends to
build up a black coating by prolonged exposure to the air. The cleaning
process involves removal of the oxide layer by dipping the material in
dilute sulphuric acid bath, which is usually reused quite a few times
before its disposal as a waste. As a result the solution is loaded up
with pollutant material such as chromium and high concentration of
copper and zinc. Due to its environmentally hazardous and acidic nature
it cannot be disposed off without pretreatment. The general treatment
of this kind of liquid effluent includes the neutralization by lime.
However, this process requires a large amount of alkali/lime resulting
in the loss of metal values as well. For the disposal of such industrial
wastes, alternate options are increasingly being applied which involves
the recovery of the heavy metals as value added products by hydromet-
allurgical methods in recent years. Recovery of heavy metals as valuable
products not only reduces the toxicity of the waste to be disposed off
but also conserves natural resources in terms of resource recovery
⁎ Corresponding author.
E-mail address: sushanta_sk@yahoo.com (S.K. Sahu).
from the waste streams (Silva et al., 2005). Thus the processing of
brass pickle liquor by hydrometallurgical route will definitely provide
economic benefits in terms of recovery of value added products of cop-
per and zinc and mitigate the pollution problem arsing due to conven-
tional disposal of waste brass pickle liquor.
A number of studies have been reported on the recovery of heavy
metals from various waste/secondary resources such as pickle liquors,
spent electrolytes, industrial effluents, and brass ash leach liquor.
(Sinha et al., 2014; Meshram et al., 2013; Nathsarma, 2002). In all
these studies solvent extraction plays a major role in producing high
pure precursor solution which is used for making high value products
of the heavy metals viz., metal powders, metal oxide powders or salts.
Recovery of base metals from copper smelter slag by oxidizing leaching
and solvent extraction has been reported by Banza et al. (2002). In this
study copper from the leach solution was recovered by solvent extrac-
tion with LIX 984 whereas, cobalt and zinc were recovered by solvent
extraction with D2EHPA. From the separated solutions metals by
electrowinning or metal salts by evaporation-crystallization could be
prepared. Sahu et al. (2008) have reported the separation of hexavalent
chromium and zinc from electroplating effluent by solvent extraction
with tri-n-butyl phosphate and selective stripping with dil. sulphuric
acid and sodium hydroxide solutions, respectively. Agrawal et al.
(2008) have developed a SX-EW (Solvent extraction-Electrowinning)

http://dx.doi.org/10.1016/j.hydromet.2015.09.012
0304-386X/© 2015 Elsevier B.V. All rights reserved.

Please cite this article as: Sinha, M.K., et al., Recovery of high value copper and zinc oxide powder from waste brass pickle liquor by solvent
extraction, Hydrometallurgy (2015), http://dx.doi.org/10.1016/j.hydromet.2015.09.012
2 M.K. Sinha et al. / Hydrometallurgy xxx (2015) xxx–xxx

process to recover high value copper and nickel powder from the
copper bleed solution. Recently, Meshram et al. (2013) have extensively
reported the solvothermal synthesis of high value copper powder from
copper bleed solution of an Indian copper smelter using Versatic 10 acid
as an extractant.
Oxime extractants of LIX series are considered to be among
the best reagents for the extraction of base metals because of their
performance such as excellent phase separation, low entrainment loss
to the raffinate, rapid metal transfer kinetics and high extractive
strength. Besides, they do not promote excessive crud formation.
The LIX reagents have therefore, been extensively applied for copper
extraction in the moderately acidic conditions (Lazarova and Lazarova,
2005). Out of several variants of LIX reagents, LIX 984 (Miguel et al.,
1997; Kongolo et al., 2003; Zhuo-yue et al., 2005; Jian-she et al., 2002;
Dara and Benamor, 2002), LIX 984N (Lazarova and Lazarova, 2005;
Sridhar et al., 2009; Sridhar and Verma, 2011a, 2011b) and LIX

Table 1
Comparative study of present study with the previously reported data on the solvent extraction of Cu–Zn using LIX 984N.

Sources Composition (kg/m3) Key Findings References

Basic study for the SX of Cu at pH 2.0 using different LIX based

Synthetic nitrate solution
Synthetic sulphate bioleaching
solution
Sulphate leachate of zinc slag
Synthetic sulphate solution
Synthetic ammoniacal/ammonium
carbonate medium
Synthetic sulphate solution
Synthetic Sulphate solution
Polymetallic sea nodules
digested in 50% H2SO4
Nitrate leach solutions
of waste PCBs
Synthetic sulphate solution
(composition similar to the
plating wastewater)
Sulphate leach liquors
Synthetic chloride solution
Waste Brass pickle liquor
5.0 Cu
10.0 Cu and 20.4 Fe
7.66 Cu, 92.75 Zn and 54.42 Cd
2.5 Cu in presence of Zn,
Fe and Mn
3.0 each of Cu and Ni with
60 kg/m3 ammonium carbonate
0.2 Cu
0.15 Cu, 0.14 Ni, 0.16 Zn
0.360 Cu, 0.365 Ni and 0.040 Co
42.11 Cu, 2.12 Fe, 4.02 Pb,
1.58 Zn and 0.4 Ni
1.27 Cu and 1.17 Ni
25–27 Cu, ~30 Fe(T), 1.4–1.9 Zn,
0.06–0.1 Co and 0.02–0.03 Ni
75.6 Cu, 9.78 Fe, 1.95 Zn,
0.918 Pb, 0.906 Ni, 1.02 Cd,
0.101 Cr, 0.173 Hg, 0.046 Ag,
0.052 As and 0.061 Sb
35 Cu, 30 Zn, 1.5 Fe, 0.75 Cr,
0.03 Ni and 70 H2SO4
reagents (5% (v/v)); Extraction trend: LIX 65N b LIX 84N b LIX
Lazarova and Lazarova, 2005
984N b LIX 860N-I. Negative ΔGo with LIX 984N indicates the
extraction of Cu from nitrate media at low pH values.
Achieved high separation factor (βCu/Fe) with 10% LIX 984N at
pH 1.5, O/A 1; 98.5% Cu extracted along with b20% Fe;
Quing-ming et al., 2008
Cu stripping: 97.8% along with 30% Fe with
1.5 kg/m3 H2SO4 at O/A = 1:2.
Selective extraction (extraction yield: 87.3%) of Cu with
25% (v/v) LIX 984N at O/A = 3:2, pH 1.7. Zn and Cd separation
Xie et al., 2008
feasibility tested by D2EHPA, D2EHPA-TBP
and HEHEP at pH 2.0
Separation factor calculated at total metal concentration of
2.5 kg/m3 using 18% (v/v) LIX 984N at O/A = 1, pH 2. Extraction
order: Cu(II) N Fe(III) N Mn(II) N Fe(II) N Zn(II) at pH 2. Highest Asghari et al., 2009
separation factor: βCu/Mn = 37, βCu/Zn = 149, βCu/Fe(III) = 17.70,
βCu/Fe(II) = 396 at 1.0 kg/m3 Cu and 1.5 kg/m3 of each metal ions.
Cu and Ni co-extracted using 20% (v/v) LIX 984N in 2-stages
at A/O = 1.9:1, pH 9.2; After ammonia scrubbing at pH 7,
Sridhar et al., 2009
Ni selectively stripped using 9.8 g/L H2SO4 in 3-stages at A/O = 1;
Cu stripping with 180 kg/m3 H2SO4 in 2-stages at A/O = 1
Examined the synergistic extraction of Cu with Cyanex 301 and
LIX 984N. Maximum synergism obtained at 1:1 ratio of Cyanex
301:LIX 984N. Distribution coefficients increased with the initial
Fouad, 2009
Cu concentration and temperature. Complete Cu extraction in
2-stages at pH 0.24; 90.65% Cu stripped with 6 M HCl and then it
decreases because of formation of easily extractable chlorocomplex.
Cu, Ni and Zn extracted at different pH values using
LIX 984N = 0.05 M; Cu: 2-stages at A/O = 5.5:1, pH = 3.5;
Ni: 2-stages at A/O = 4:1, pH = 7.3; Zn: 2-stages at Sridhar and Verma, 2011a
A/O = 2:1, pH = 8.8; quantitative stripping of Cu and Ni with
2 M H2SO4 and Zn with 3 M H2SO4
Acid neutralized by alkali, Fe precipitated at pH 4.5 and Co(II)
converted to Co(III). Cu & Ni co-extracted with 10% LIX 984N
leaving Co(III) in the raffinate at A/O = 1 in 8-contacts. After
Sridhar and Verma, 2011b
ammonia scrubbing at pH 4, Ni and Cu selectively stripped using
10 kg/m3 and 180 kg/m3 H2SO4 in 2-contacts. Experiment also
performed with ACORGA M5640.
99.7% Cu extracted with 1–4 ppm of Zn, Fe, Pb in 3-stages at
O/A = 1.5:1, pH 1.5 using 50% (v/v) LIX 984N; Cu stripping: N97%
Le et al., 2011
in 4-stages at O/A = 2:1 with spent electrolyte containing
320 kg/m3 H2SO4 and 30.01 kg/m3 Cu.
With 15% (v/v) LIX 984N, 92.9% Cu extracted at pH
4 & O/A = 1:1; 93% Ni extracted
with 15% (v/v) LIX 984N at pH 10.5 & O/A = 1:1; Cu Liqing et al., 2011
stripping: N99.1% with 170 kg/m3 H2SO4 at O/A = 1:2; Ni stripping:
99.3% with 200 kg/m3 H2SO4 at O/A = 1:2
Tested extraction behaviour for Cu with LIX 984N, LIX 612N-LV
and Acorga M5640. Acid neutralized by alkali. Only 86% Cu
Ochromowicz and
extracted in 2-stages at O/A = 4:1, pH 2.2. Fe co-extracted with
Chmielewski, 2013
Cu in LIX 984N. Extraction trend [with 30% (v/v) solvent]:
Acorga M5640 N LIX 612N-LV N LIX 984N.
Fe extraction increased with decreasing Cu extraction. Cu/Fe
ratio in the organic solution increased with increasing Cu
extraction as Fe extraction decreased. Order of loading capacity
Lu and Dreisinger, 2013
of Cu: LIX 984 N LIX612N-LV, XI04003 N LIX84-I
[extractants = 40% (v/v)]; optimum conditions for Cu extraction
with low Fe co-extraction: A/O = 2:1, pH b 0.5, T = 40 °C.
Acid and Fe removed by SX and precipitation, respectively before
extraction of Cu and Zn. Bench scale results applied in lab scale
mixer settler unit. Cu selectively extracted at pH 2.5 in 2-stages
Present study
at O/A 2/1. After Cr precipitation Zn quantitatively extracted
at pH 5.5 in 2-stages at O/A 2/1. Stripped solutions used for
hydrothermal synthesis of Cu powder and ZnO particles.

Please cite this article as: Sinha, M.K., et al., Recovery of high value copper and zinc oxide powder from waste brass pickle liquor by solvent
extraction, Hydrometallurgy (2015), http://dx.doi.org/10.1016/j.hydromet.2015.09.012
 M.K. Sinha et al. / Hydrometallurgy xxx (2015) xxx–xxx
984N-C (Panda et al., 2012; Kul and Çetinkaya, 2009) have been found
to be the quite effective for copper extraction. Use of a synergistic
mixture of LIX 984N with Cyanex 301 for copper extraction has also
been investigated (Fouad, 2009). In fact, the selective extraction of
copper over other heavy metal ions (Ni, Fe and Zn) from various
media including acidic waste/leach solutions using LIX 984N, has been
reported by several researchers as summarised in Table 1. Quing-ming
et al. (2008) reported the extraction of copper from synthetic solution
similar to the bioleach liquor of a copper mine (10 kg/m3 Cu and
20.4 kg/m3 Fe, pH 2) using 10% LIX 984N and efficient stripping of
loaded organic using 1.5 M H2SO4. Similarly, separation of Cu and Zn
from the sulphate leach liquor of a zinc slag (Xie et al., 2008) and
from a synthetic solution with LIX 984N (Asghari et al., 2009) was
also elaborated. Le et al. (2011) reported the recovery of copper with
50% LIX 984N from the leach solutions of waste PCBs containing
42.11 kg/m3 Cu along with other metals at initial pH 1.5 in nitrate
medium. Separation of Cu and Ni from sulphate medium with LIX
984N was examined (Liqing et al., 2011) with the aim of processing
the plating wastewater; the optimum pH values for Cu and Ni extrac-
tion were found to be 4 and 10.5, respectively. Selective extraction of
Ni over Zn and Cd from the sulphate leach solution of cold purification
filtration cake of zinc hydrometallurgical plant using 10% LIX 984N at
pH 5.3 and O/A ratio of 2, was studied by Balesini et al. (2013). The ex-
traction efficiency of LIX 984N for copper with respect to other chelating
extractants was also reported (Ochromowicz and Chmielewski, 2013;
Lu and Dreisinger, 2013).
Nano-materials/powders have gained considerable attention due
to their unique properties and wide application area. Among various
nanoparticles, metallic Cu powder and ZnO nanoparticles are extensively
popular, which may be due to their excellent optical, electrical and
thermal properties, catalytic activities as well as cost effectiveness.
Various chemical, physical, and electrochemical methods such as,
hydrothermal/solvothermal synthesis, sol–gel, microwave/ultrasound-
assisted synthesis, thermal decomposition, electrodeposition, and
chemical vapour deposition process, have been applied for the
synthesis of Cu/ZnO nanomaterials (Benhebal et al., 2013; Hu et al.,
2004; Peulon and Lincot, 1996; Wei et al., 2009; Ni et al., 2005;
Shah and Al-Ghamdi, 2011; Meshram et al., 2013). Among the
reported methods, hydrothermal process has been considered as a sim-
ple way to synthesize the nano-powders because of the involvement of
easy and low-cost procedures, moderate temperature, great control
over experimental parameters and convenience for the synthesis on
large scale (Sinha et al., 2015; Natrchalayuth et al., 2012; Pandey et al.,
2000; Agrawal et al., 2006a).
It is observed from the literature survey (Table 1) that the previous
investigations were mainly based on the basic study for determining
the optimum parameters particularly for the extraction of copper with
LIX 984N. Although, a few reports are available on the extraction and
separation of Cu with other metal ions from original leach solutions,
but these are restricted to study the copper purification steps only.
Therefore, the present investigation is aimed at developing a complete
process for the extraction and separation of copper and zinc from
brass pickle liquor using LIX 984N, and synthesis of high value products
such as copper powder and zinc oxide particles utilizing the purified
solution by hydrothermal precipitation route. The prepared copper
and zinc oxide particles were characterized by chemical analysis, SEM
and XRD-EDS studies. A process flow-sheet for the recovery of metal
values from the spent brass pickle liquor is also given.
2. Materials and method
Spent brass pickle liquor containing 35 kg/m3 Cu, 30 kg/m3 Zn,
70 kg/m3 H2SO4, 1.5 kg/m3 Fe (Total), 0.75 kg/m3 Cr and 0.03 kg/m3
Ni was collected from a local brass industry (Jharkhand, India) to
recover value added products of copper and zinc from it. Prior to
the recovery of copper and zinc, sulphuric acid from the pickle liquor
Please cite this article as: Sinha, M.K., et al., Recovery of high value copper and zinc oxide powder from waste brass pickle liquor by solvent
extraction, Hydrometallurgy (2015), http://dx.doi.org/10.1016/j.hydromet.2015.09.012
3
was recovered by solvent extraction with tris-2-ethylhexyl amine
(TEHA) and there after iron was removed by precipitation at pH 3.5.
During the acid recovery and iron precipitation loss of copper and zinc
due to co-extraction and adsorption on the surface of the precipitated
iron hydroxide was almost negligible. Acid and iron depleted waste
pickle liquor containing 35 kg/m3 Cu(II), 30 kg/m3 Zn(II), 0.75 kg/m3
Cr(III) and 0.03 kg/m3 Ni(II) was then treated for the extractive
separation of copper and zinc using LIX 984N (1:1 mixture of
5-nonyl salicylaldoxime and 2-hydroxy-5-nonylacetophenone oxime)
as extractants in kerosene. However, in order to optimize the extraction
conditions a synthetic sulphate solution containing 35 kg/m3 Cu or
30 kg/m3 Zn was prepared by dissolving their respective sulphate
salts (CuSO4·5H2O and ZnSO4·7H2O). The extractant LIX 984N was
supplied by Cognis, Germany and used for the extraction studies
without further purification. All other chemicals used in this study
were analytical grade reagents.
Solvent extraction experiments were carried out by equilibrating
equal volumes (except for the construction of McCabe–Thiele diagram)
of aqueous solution and the extractant, LIX 984N of known concentra-
tion in a stoppered vial using rotospin shaker at 50 rpm. The shaking
time of 15 min was found to be sufficient to reach equilibrium. The pH
of the aqueous solution was adjusted to the desired value by adding
dilute H2SO4 or NaOH solutions. After phase disengagement aqueous
and organic phases were separated. Metal ions concentration in the
aqueous phase was analysed by Atomic Absorption Spectrometer
(Model: ElementAs AAS4141). Metal content in the organic phase
was determined by mass balance. Stripping studies of metal ions from
the loaded organic was carried out with the dilute sulphuric acid of a
known concentration.
The high purity copper powder was prepared by the hydrogen
reduction of stripped copper solution in an autoclave (titanium
vessel-1 L capacity). The copper solution (500 mL) of known compo-
sition was heated to the desired temperature, and then hydrogen gas
was introduced at a predetermined pressure which was maintained
throughout the gaseous reduction. At the end of reduction process,
the autoclave was cooled to room temperature. The copper powder
produced was filtered over a Buchner funnel using Whatman paper
(no. 41), washed with distilled water and rinsed with sodium
potassium tartrate solution (2 wt.%) to inhibit the surface oxidation
because the synthesized copper powder is susceptible to oxidation
(Bagchi et al., 2012). The copper powder thus obtained was dried in
an oven at 80 °C overnight. Further, the dried powder was annealed in
Fig. 1. Effect of pH on the solvent extraction of copper and zinc. Aq. phase: 35 kg/m3 Cu,
30 kg/m3 Zn, Org. phase: 1 M LIX 984N in kerosene, Phase ratio: 1:1.
4 M.K. Sinha et al. / Hydrometallurgy xxx (2015) xxx–xxx
Fig. 2. Stripping of metal ions from the loaded solvents in single contact. LIX 984N:
34.95 kg/m3 Cu, 29.70 kg/m3 Zn, H2SO4: Different Concentration, Phase ratio: 1:1.
an electrically operated tubular furnace with a flow of hydrogen gas at
the desired temperature for proper granulometry, long term storage
and prevention of oxidation (Bagchi et al., 2012).
In order to prepare the high purity zinc oxide powder, pH of the
stripped solution containing zinc was increased by adding 1 M NaOH
solution dropwise (3 mL/min) with a constant stirring. When the
desired pH (~12) was reached, the solution (500 mL) was autoclaved
under the nitrogen atmosphere for 2 h at a pre-set temperature and
pressure. The precipitate of ZnO so obtained was cooled and filtered,
washed with distilled water and acetone (~50 ml in each experiment);
and dried in an oven at 80 °C overnight.
The as-prepared copper metal powder and zinc oxide particles were
characterized by chemical analysis, XRD and SEM-EDS studies. The XRD
data were recorded (Bruker D8-discover) using CuKα radiation in the
2θ range of 10–90o. The powder sample was put on a grid and was
coated with gold before recording the SEM (Nova Nano SEM 430).
Fig. 3. Effect of O/A ratio on the extraction of copper and zinc. Aq. phase: 35 kg/m3 Cu
and 30 kg/m3 Zn, Org. phase: 1 M LIX 984N in kerosene. Eq. pH = 2.5 for Cu and
Eq. pH = 5.5 for Zn.
Please cite this article as: Sinha, M.K., et al., Recovery of high value copper and zinc oxide powder from waste brass pickle liquor by solvent
extraction, Hydrometallurgy (2015), http://dx.doi.org/10.1016/j.hydromet.2015.09.012
Fig. 4. McCabe–Thiele Plot for the extraction of copper with LIX 984N. Aq. phase: 35 kg/m3
Cu and 30 kg/m3 Zn, Org. phase: 1 M LIX 984N in kerosene, Eq. pH = 2.5.
3. Results and discussion
3.1. Removal of acid and iron from the pickle liquor
In order to remove/recover acid from the pickle liquor the model
solution containing 35 kg/m3 Cu, 30 kg/m3 Zn , 70 kg/m3 H2SO4, 1.5 kg/m3
Fe (Total), 0.75 kg/m3 Cr and 0.03 kg/m3 Ni was equilibrated with
40% (v/v) TEHA in kerosene at phase ratio of 2:1. It was observed
that almost total acid was extracted into the organic phase in a single
contact. It was also noticed that no copper and zinc was co-extracted
into the organic phase which may be due to the less affinity of TEHA
towards copper and zinc as sulphate. The loaded TEHA was regenerated
by stripping with distilled water at 50 °C at a phase ratio (O/A) of unity.
It was found that complete H2SO4 were stripped from the loaded TEHA
in 2 contacts. Iron from the acid depleted brass pickle liquor was
removed by precipitation at pH N3.5. During the precipitation of iron,
co-precipitation of copper and zinc was not observed.
Fig. 5. McCabe–Thiele Plot for the extraction of zinc with LIX 984N. Aq. phase: 30 kg/m3 Zn,
Org. phase: 1 M LIX 984N in kerosene, Eq. pH = 5.5.
 M.K. Sinha et al. / Hydrometallurgy xxx (2015) xxx–xxx
Fig. 6. Counter-current simulation for the extraction of copper with LIX 984N.
Aq. phase: 35 kg/m3 Cu and other metal ions, Org. phase: 1 M LIX 984N in kerosene,
O/A = 2:1, Eq. pH = 2.5.
3.2. Solvent extraction of copper and zinc with LIX 984N
Acid and iron depleted brass pickle liquor contained 35 kg/m3 Cu(II),
30 kg/m3 Zn(II), 0.75 kg/m3 Cr and 0.03 kg/m3 Ni. In order to establish
the separation of copper and zinc from the above solution, a synthetic
solution of similar composition (35 kg/m3 Cu(II) and 30 kg/m3 Zn(II))
was used to extract Cu/Zn by equilibrating the solution at the desired
pH with 30% LIX 984N (~1 M) in kerosene as the diluent at the phase
ratio (O/A) of 1:1 and 30 °C for 15 min. Extraction of copper increased
from 10 to 99% in the equilibrium pH range 1.5 to 3.9 without any
co-extraction of zinc. Extraction of zinc started at equilibrium pH
above 4.5 and increased from 5 to 95% in the equilibrium pH
range 4.8 to 6.4 (Fig. 1). The respective pH1/2 values (pH1/2 = the
pH corresponding to the extraction of 50% of the metal ions into
the organic phase) for Cu and Zn were found to be 2.5 and 5.5. Thus
it is clear that 1 M LIX 984N is adequate for selective extraction of
copper over zinc with a ΔpH1/2(Zn–Cu) of 3.0, and there is no chance
of mutual contamination of one metal with the other during their
solvent extraction with LIX 984N.
The saturation loading capacity of LIX 984N for Cu (at equilibrium
pH 2.5) and Zn (at equilibrium pH 5.5) was also determined separately
by repetitive contact of the same organic phase with the fresh aqueous
solution at phase ratio 1 until the metal concentration in the raffinate
was the same as that of the aqueous feed. The loading capacity of LIX
984N was found to be 34.95 kg/m3 for Cu and 29.70 kg/m3 for Zn after
four stages.
Stripping of copper/zinc was carried out using meal saturated/
loaded LIX 984N containing 34.95 kg/m3 Cu or 29.70 kg/m3 Zn with
different concentrations of sulphuric acid (0.25–1.5 M) at O/A
phase ratio of 1. Stripping of both the metal ions increased with an
increase in the sulphuric acid concentration (Fig. 2) and with 1.5 M
sulphuric acid both the metal ions were stripped quantitatively in a
single stage.
Fig. 7. Counter-current simulation for the extraction of zinc with LIX 984N. Aq. phase: 30 kg/m3 Zn and 0.03 kg/m3 Ni, Org. phase: 1 M LIX 984N in kerosene, O/A = 2:1, Eq. pH = 5.5.
Please cite this article as: Sinha, M.K., et al., Recovery of high value copper and zinc oxide powder from waste brass pickle liquor by solvent
extraction, Hydrometallurgy (2015), http://dx.doi.org/10.1016/j.hydromet.2015.09.012
5
3.3. Extraction isotherm and McCabe–Thiele diagram
The extraction isotherm for copper was obtained by contacting a
mixed solution containing 35 kg/m3 Cu and 30 kg/m3 Zn with 1 M LIX
984N in kerosene at different O/A phase ratios (O/A = 1:5 to 5:1) and
the equilibrium pH of 2.5. Extraction of copper increased from 18 to
99.9% with the increase in phase ratio. At the entire phase ratio
co-extraction of zinc with copper was not observed. The raffinate
after complete extraction of copper was used to obtain extraction
isotherm for zinc by contacting with 1 M LIX 984N at different phase
ratios (O/A = 1:5 to 5:1) and equilibrium pH of 5.5. In the above
range of phase ratios zinc extraction increased from 18 to 92.5% (Fig. 3).
Using the extraction data obtained from the phase ratio variation,
McCabe–Thiele diagram was drawn to determine the number of theo-
retical counter-current stages required for complete extraction of
copper and zinc. It was found from this diagram that two counter-
current extraction stages were sufficient for complete extraction of
copper with 1 M LIX 984N at a phase ratio of 2:1 and equilibrium
pH 2.5 (Fig. 4). On the other hand three counter-current stages were
required for the complete extraction of zinc with 1 M LIX 984N at the
phase ratio of 2:1 and equilibrium pH of 5.5 (Fig. 5). Simulation of
counter-current extraction of copper or zinc with 1 M LIX 984N
(Figs. 6 and 7) showed that at the end of the second stage 17.5 kg/m3
copper and at the end of third stage 14.99 kg/m3 zinc were loaded
into the organic phase.
The above optimized conditions were applied to separate copper
and zinc from the spent brass pickle liquor [35 kg/m3 Cu, 30 kg/m3 Zn,
0.75 kg/m3 Cr and 0.03 kg/m3 Ni] in a laboratory scale mixer settler
unit using 1 M LIX 984N in kerosene as the extractant. Before proceed-
ing for mixer settler operation, sulphuric acid and iron were removed
from the pickle solution as described in Section 3.1. The resulting
Fe(OH)3 precipitate can be stored and processed for the production of
pigment. The flow rates of aqueous and organic phase were maintained
according to the requirements of the phase ratio (O/A), which was
2:1 as mentioned above. The pH of the solution in every extraction
step was maintained to the desired level using required amount of
dilute NaOH solution. In the case of extraction of Cu(II) the organic
and aqueous flow rates were maintained at 8.12 L/h and 4.05 L/h,
respectively at equilibrium pH of 2.5. At the end of the second stage
17.5 kg/m3 Cu was loaded into the organic phase with no contamination
of Zn, Cr and Ni. Before zinc extraction chromium from the copper free
raffinate was completely removed by precipitation at pH 5.3 using 10%
ammonia solution in the presence of ammonium chloride at room tem-
perature (Mahmoud and Barakat, 2001); negligible loss of Zn and Ni
was observed in to the precipitate. The resulting hydroxide precipitate
of chromium can be used as colouring agent/pigment or as catalyst for
organic reactions. After chromium removal the solution [30 kg/m3
Zn(II) and 0.03 kg/m3 Ni] was subjected to solvent extraction of zinc
in the mixer settler unit at the equilibrium pH 5.5 and O/A ratio of
2:1 (flow rates of organic = 8.12 L/h and aqueous = 4.05 L/h). After
three stages of counter-current extraction 14.99 kg/m3 zinc was loaded
in to the organic phase leaving nickel in the raffinate.
6 M.K. Sinha et al. / Hydrometallurgy xxx (2015) xxx–xxx

Fig. 10. XRD of ZnO powder produced.

Fig. 8. XRD of copper powder produced by pressure hydrogen stripping.

The high loading of copper and zinc in the two streams of the
extractants, is beneficial for the synthesis of the value added products
from the respective stripped solutions of high metal concentration.
The results show that copper and zinc were completely stripped with
150 kg/m3 sulphuric acid solutions from their respective loaded organic
phases at O/A ratio of 1:1 in a single stage.
3.4. Synthesis of the value added products
3.4.1. Hydrothermal synthesis of copper powder
The purified copper and zinc solutions generated in the processing of
spent brass pickle liquor by solvent extraction with LIX 984N as
discussed above, were used for the synthesis of high purity copper
metal powder and zinc oxide particles. Copper powder was produced
by the reduction of Cu2+ ions present in the purified copper sulphate
solution under hydrogen atmosphere in an autoclave at 20 bar H2 pres-
sure, 423 K and 400 rpm for 2 h. The hydrothermal reduction of copper
at high temperature and hydrogen pressure from highly acidic copper
bleed solution generated from electrolytic unit of copper smelter has
been successfully explored and described previously in detail by our re-
search group at CSIR-NML (Agrawal et al., 2006b). From the pressure
and temperature optimization experiments it was concluded that the
high temperature and hydrogen pressure were preferred and necessary
to enhance reduction kinetics. In the beginning, 1 g copper powder was
also added as a seed to accelerate the reaction rate and to avoid copper
plating on the stirrer and interior of the reaction vessel (Meshram et al.,
2013). Copper seed acts as heterogeneous nucleating site for the
nucleation of copper, which have comparatively low energy require-
ment than that of homogeneous nucleation. This enhances the overall
reaction rate and prevents copper plating on the vessel. After the exper-
iment the aqueous filtrate was analysed for copper which was found to
be 0.08 kg/m3; the filtrate can be recycled back to the copper stripping
circuit. Under the above conditions the recovery of copper as powder
was found to be 99.5%. The copper powder obtained was filtered,
washed and dried as mentioned earlier before it was annealed at 500 °C
in a tubular furnace with a flow of hydrogen gas (5 L/min). The overall re-
duction of copper sulphate solution to copper powder can be represented
as (Agrawal et al., 2006a):
Cu2þ þH2 →CuHþ þHþ ð1Þ
CuHþ þCu2þ →2Cuþ þHþ ð2Þ

Fig. 9. SEM and EDS of copper powder after annealing.

Please cite this article as: Sinha, M.K., et al., Recovery of high value copper and zinc oxide powder from waste brass pickle liquor by solvent
extraction, Hydrometallurgy (2015), http://dx.doi.org/10.1016/j.hydromet.2015.09.012
 M.K. Sinha et al. / Hydrometallurgy xxx (2015) xxx–xxx 7

Fig. 11. SEM and EDS of as-prepared ZnO powder.

Fig. 12. Flow sheet for the recovery of metal values from the brass pickle liquor.

Please cite this article as: Sinha, M.K., et al., Recovery of high value copper and zinc oxide powder from waste brass pickle liquor by solvent
extraction, Hydrometallurgy (2015), http://dx.doi.org/10.1016/j.hydromet.2015.09.012
8 M.K. Sinha et al. / Hydrometallurgy xxx (2015) xxx–xxx
Cuþ þH2 →CuH þ Hþ
CuH þ Cuþ →2Cu þ Hþ
The annealed copper powder was characterized by SEM and XRD.
The XRD pattern (Fig. 8) of the copper particles shows the presence of
only copper phase as all the peaks agreed well with the reported data
for pure copper (JCPDS file No. 04–0836). The sharp diffraction peaks
imply that the copper powder has good crystallinity. The purity of the
synthesized Cu powder (chemical analysis) was found to be 99.9%
with impurity content of 0.015% Zn, 0.018% Fe and 0.005% Ni. The SEM
image (Fig. 9a) of the synthesized copper powder after annealing
shows that the particle size ranges between 50 and 100 μm with
globular shape. High purity of the as-synthesized copper powder is also
confirmed by the EDS (Fig. 9b). The copper powder has characteristics
suitable for the powder metallurgical (P/M) applications.
3.4.2. Hydrothermal synthesis of ZnO powder from the stripped solution
In order to synthesize the ZnO powder, the pH of the purified
solution containing 14.99 kg/m3 Zn was raised to 12 by slow addition
of 1 M NaOH with constant stirring. The highly basic pH was chosen
to ensure product purity and faster growth rate of the zinc oxide
particles (Ikono et al., 2012; Baruah and Dutta, 2009; Wu et al., 2011;
Wahab et al., 2009a, 2009b; Lu and Yeh, 2000).The precursor solution
was then autoclaved at 423 K with stirring at 400 rpm for 2 h under
the autogenous pressure (4 bar). The particles obtained was filtered,
washed with distilled water and dried overnight in an electrical oven
at 80 °C. The hydrothermal conversion of zinc sulphate solution to
ZnO can be expressed as (Aimable et al., 2010):
Zn2þ þ4OH‐ →ZnðOHÞ4 2‐
ZnðOHÞ4 2‐ →ZnO þ 2OH‐ þH2 O
At the highly basic conditions, Zn(OH) 24 − species is formed
(Aimable et al., 2010; Ma et al., 2005) in the solution and under
hydrothermal condition it will dissolve to form Zn2 + and OH− ions.
When the ionic product of Zn2 + and OH− exceeds a critical value
under supersaturation condition, ZnO nuclei precipitate from the
solution and crystal growth begins.
The ZnO powder produced was then characterized by SEM and
XRD. The sharp X-ray diffraction peaks of hydrothermally prepared
powder confirmed that the synthesized ZnO-material was pure and
had good crystallinity. All diffraction peaks in the XRD pattern of
as-prepared zinc oxide agreed well with the reported data (JCPDS
file No. 05–0664) for pure ZnO of hexagonal wurtzite structure
(Fig. 10). The purity of the as-produced ZnO powder was found to
be N99% as determined by chemical analysis with a yield of ~ 80%
Zn. SEM image (Fig. 11a) of ZnO shows that particle size of agglom-
erated zinc oxide particles ranges between 0.5 and 1 μm with a rice
grain shape. The SEM-EDS analysis (Fig. 11b) clearly shows that the
sample prepared by the above route has pure ZnO phase. The waste
solution after recovering ZnO needs to be further treated to precipitate
residual zinc before it is discharged or recycled.
4. Conclusions
A complete process has been developed to separate and recover
copper and zinc from the spent brass pickle liquor by solvent extraction
followed by hydrothermal reduction/precipitation route to produce
value added products. A process flow-sheet has been worked out to
recover metal values (Fig. 12). Copper and zinc from the spent brass
pickle liquor containing 35 kg/m3 Cu, 30 kg/m3 Zn, 0.75 kg/m3 Cr and
0.03 kg/m3 Ni were separated by using LIX 984N. Based on the bench
scale results, experiments were also performed in laboratory scale
mixer settler unit.
Please cite this article as: Sinha, M.K., et al., Recovery of high value copper and zinc oxide powder from waste brass pickle liquor by solvent
extraction, Hydrometallurgy (2015), http://dx.doi.org/10.1016/j.hydromet.2015.09.012
ð3Þ The following conclusions have been drawn:
ð4Þ • LIX 984N was found to be selective for copper extraction at lower pH
(ΔpH1/2 = 3.0) whereas zinc extraction achieved at higher pH.
• The number of counter-current stages for extraction of copper and
zinc was determined from the McCabe–Thiele plots. Copper was
completely extracted in two counter-current stages in a laboratory
scale mixer settler unit using 1 M LIX 984N at equilibrium pH 2.5
and phase ratio (O/A) 2/1.
• Zinc was extracted from the copper free raffinate followed by
chromium removal, in three counter-current stages using 1 M LIX
984N at the equilibrium pH 5.5 and phase ratio (O/A) 2/1.
• From the respective metal loaded organics, copper and zinc were
stripped with 150 kg/m3 H2 SO 4 solutions. The globular shaped
(50–100 μm size) copper powder of high purity (99.9%) was
synthesized from the purified copper solution in an autoclave by
hydrogen reduction at 20 bar pressure (H2), 423 K and 400 rpm.
• High pure zinc oxide particles of rice grain shape (0.5–1 μm size) were
synthesized by hydrothermal precipitation at 423 K and pH 12. The
synthesized copper metal powder and zinc oxide particles were
characterized by chemical analysis, XRD and SEM-EDS studies, and
can be used for various applications.
Acknowledgements
Authors are thankful to the Director of the CSIR-National Metallurgical
Laboratory (NML), Jamshedpur, India for giving permission to publish the
paper. Thanks are also due to DST, Govt. of India for sponsoring the project
ð5Þ under RFBR (Russia)-DST (India) bilateral programme (Grant no. INT/
RFBR/P-29/2008).
ð6Þ
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