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 from the waste streams (Silva et al., 2005). Thus the processing of
brass pickle liquor by hydrometallurgical route will definitely provide
Industrial wastes generated in metallic industries are generally economic benefits in terms of recovery of value added products of cop-
laden with heavy metals. Brass pickle liquor is also a kind of industrial per and zinc and mitigate the pollution problem arsing due to conven-
waste generated during cleaning of the brass surface which tends to tional disposal of waste brass pickle liquor.
build up a black coating by prolonged exposure to the air. The cleaning A number of studies have been reported on the recovery of heavy
process involves removal of the oxide layer by dipping the material in metals from various waste/secondary resources such as pickle liquors,
dilute sulphuric acid bath, which is usually reused quite a few times spent electrolytes, industrial effluents, and brass ash leach liquor.
before its disposal as a waste. As a result the solution is loaded up (Sinha et al., 2014; Meshram et al., 2013; Nathsarma, 2002). In all
with pollutant material such as chromium and high concentration of these studies solvent extraction plays a major role in producing high
copper and zinc. Due to its environmentally hazardous and acidic nature pure precursor solution which is used for making high value products
it cannot be disposed off without pretreatment. The general treatment of the heavy metals viz., metal powders, metal oxide powders or salts.
of this kind of liquid effluent includes the neutralization by lime. Recovery of base metals from copper smelter slag by oxidizing leaching
However, this process requires a large amount of alkali/lime resulting and solvent extraction has been reported by Banza et al. (2002). In this
in the loss of metal values as well. For the disposal of such industrial study copper from the leach solution was recovered by solvent extrac-
wastes, alternate options are increasingly being applied which involves tion with LIX 984 whereas, cobalt and zinc were recovered by solvent
the recovery of the heavy metals as value added products by hydromet- extraction with D2EHPA. From the separated solutions metals by
allurgical methods in recent years. Recovery of heavy metals as valuable electrowinning or metal salts by evaporation-crystallization could be
products not only reduces the toxicity of the waste to be disposed off prepared. Sahu et al. (2008) have reported the separation of hexavalent
but also conserves natural resources in terms of resource recovery chromium and zinc from electroplating effluent by solvent extraction
with tri-n-butyl phosphate and selective stripping with dil. sulphuric
⁎ Corresponding author. acid and sodium hydroxide solutions, respectively. Agrawal et al.
E-mail address: sushanta_sk@yahoo.com (S.K. Sahu). (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 to the raffinate, rapid metal transfer kinetics and high extractive
copper bleed solution. Recently, Meshram et al. (2013) have extensively strength. Besides, they do not promote excessive crud formation.
reported the solvothermal synthesis of high value copper powder from The LIX reagents have therefore, been extensively applied for copper
copper bleed solution of an Indian copper smelter using Versatic 10 acid extraction in the moderately acidic conditions (Lazarova and Lazarova,
as an extractant. 2005). Out of several variants of LIX reagents, LIX 984 (Miguel et al.,
Oxime extractants of LIX series are considered to be among 1997; Kongolo et al., 2003; Zhuo-yue et al., 2005; Jian-she et al., 2002;
the best reagents for the extraction of base metals because of their Dara and Benamor, 2002), LIX 984N (Lazarova and Lazarova, 2005;
performance such as excellent phase separation, low entrainment loss 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

reagents (5% (v/v)); Extraction trend: LIX 65N b LIX 84N b LIX
Synthetic nitrate solution 5.0 Cu 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
Synthetic sulphate bioleaching
pH 1.5, O/A 1; 98.5% Cu extracted along with b20% Fe;
10.0 Cu and 20.4 Fe Quing-ming et al., 2008
Cu stripping: 97.8% along with 30% Fe with
solution
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
Sulphate leachate of zinc slag 7.66 Cu, 92.75 Zn and 54.42 Cd 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
2.5 Cu in presence of Zn,
Synthetic sulphate solution order: Cu(II) N Fe(III) N Mn(II) N Fe(II) N Zn(II) at pH 2. Highest Asghari et al., 2009
Fe and Mn
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
Synthetic ammoniacal/ammonium 3.0 each of Cu and Ni with at A/O = 1.9:1, pH 9.2; After ammonia scrubbing at pH 7,
Sridhar et al., 2009
carbonate medium 60 kg/m3 ammonium carbonate 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
Synthetic sulphate solution 0.2 Cu 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;
Synthetic Sulphate solution 0.15 Cu, 0.14 Ni, 0.16 Zn 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
Polymetallic sea nodules leaving Co(III) in the raffinate at A/O = 1 in 8-contacts. After
0.360 Cu, 0.365 Ni and 0.040 Co Sridhar and Verma, 2011b
digested in 50% H2SO4 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
Nitrate leach solutions 42.11 Cu, 2.12 Fe, 4.02 Pb, O/A = 1.5:1, pH 1.5 using 50% (v/v) LIX 984N; Cu stripping: N97%
Le et al., 2011
of waste PCBs 1.58 Zn and 0.4 Ni 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
Synthetic sulphate solution 4 & O/A = 1:1; 93% Ni extracted
(composition similar to the 1.27 Cu and 1.17 Ni with 15% (v/v) LIX 984N at pH 10.5 & O/A = 1:1; Cu Liqing et al., 2011
plating wastewater) 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
25–27 Cu, ~30 Fe(T), 1.4–1.9 Zn, Ochromowicz and
Sulphate leach liquors extracted in 2-stages at O/A = 4:1, pH 2.2. Fe co-extracted with
0.06–0.1 Co and 0.02–0.03 Ni 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
75.6 Cu, 9.78 Fe, 1.95 Zn, ratio in the organic solution increased with increasing Cu
0.918 Pb, 0.906 Ni, 1.02 Cd, extraction as Fe extraction decreased. Order of loading capacity
Synthetic chloride solution Lu and Dreisinger, 2013
0.101 Cr, 0.173 Hg, 0.046 Ag, of Cu: LIX 984 N LIX612N-LV, XI04003 N LIX84-I
0.052 As and 0.061 Sb [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
35 Cu, 30 Zn, 1.5 Fe, 0.75 Cr, mixer settler unit. Cu selectively extracted at pH 2.5 in 2-stages
Waste Brass pickle liquor Present study
0.03 Ni and 70 H2SO4 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 3

984N-C (Panda et al., 2012; Kul and Çetinkaya, 2009) have been found was recovered by solvent extraction with tris-2-ethylhexyl amine
to be the quite effective for copper extraction. Use of a synergistic (TEHA) and there after iron was removed by precipitation at pH 3.5.
mixture of LIX 984N with Cyanex 301 for copper extraction has also During the acid recovery and iron precipitation loss of copper and zinc
been investigated (Fouad, 2009). In fact, the selective extraction of due to co-extraction and adsorption on the surface of the precipitated
copper over other heavy metal ions (Ni, Fe and Zn) from various iron hydroxide was almost negligible. Acid and iron depleted waste
media including acidic waste/leach solutions using LIX 984N, has been pickle liquor containing 35 kg/m3 Cu(II), 30 kg/m3 Zn(II), 0.75 kg/m3
reported by several researchers as summarised in Table 1. Quing-ming Cr(III) and 0.03 kg/m3 Ni(II) was then treated for the extractive
et al. (2008) reported the extraction of copper from synthetic solution separation of copper and zinc using LIX 984N (1:1 mixture of
similar to the bioleach liquor of a copper mine (10 kg/m3 Cu and 5-nonyl salicylaldoxime and 2-hydroxy-5-nonylacetophenone oxime)
20.4 kg/m3 Fe, pH 2) using 10% LIX 984N and efficient stripping of as extractants in kerosene. However, in order to optimize the extraction
loaded organic using 1.5 M H2SO4. Similarly, separation of Cu and Zn conditions a synthetic sulphate solution containing 35 kg/m3 Cu or
from the sulphate leach liquor of a zinc slag (Xie et al., 2008) and 30 kg/m3 Zn was prepared by dissolving their respective sulphate
from a synthetic solution with LIX 984N (Asghari et al., 2009) was salts (CuSO4·5H2O and ZnSO4·7H2O). The extractant LIX 984N was
also elaborated. Le et al. (2011) reported the recovery of copper with supplied by Cognis, Germany and used for the extraction studies
50% LIX 984N from the leach solutions of waste PCBs containing without further purification. All other chemicals used in this study
42.11 kg/m3 Cu along with other metals at initial pH 1.5 in nitrate were analytical grade reagents.
medium. Separation of Cu and Ni from sulphate medium with LIX Solvent extraction experiments were carried out by equilibrating
984N was examined (Liqing et al., 2011) with the aim of processing equal volumes (except for the construction of McCabe–Thiele diagram)
the plating wastewater; the optimum pH values for Cu and Ni extrac- of aqueous solution and the extractant, LIX 984N of known concentra-
tion were found to be 4 and 10.5, respectively. Selective extraction of tion in a stoppered vial using rotospin shaker at 50 rpm. The shaking
Ni over Zn and Cd from the sulphate leach solution of cold purification time of 15 min was found to be sufficient to reach equilibrium. The pH
filtration cake of zinc hydrometallurgical plant using 10% LIX 984N at of the aqueous solution was adjusted to the desired value by adding
pH 5.3 and O/A ratio of 2, was studied by Balesini et al. (2013). The ex- dilute H2SO4 or NaOH solutions. After phase disengagement aqueous
traction efficiency of LIX 984N for copper with respect to other chelating and organic phases were separated. Metal ions concentration in the
extractants was also reported (Ochromowicz and Chmielewski, 2013; aqueous phase was analysed by Atomic Absorption Spectrometer
Lu and Dreisinger, 2013). (Model: ElementAs AAS4141). Metal content in the organic phase
Nano-materials/powders have gained considerable attention due was determined by mass balance. Stripping studies of metal ions from
to their unique properties and wide application area. Among various the loaded organic was carried out with the dilute sulphuric acid of a
nanoparticles, metallic Cu powder and ZnO nanoparticles are extensively known concentration.
popular, which may be due to their excellent optical, electrical and The high purity copper powder was prepared by the hydrogen
thermal properties, catalytic activities as well as cost effectiveness. reduction of stripped copper solution in an autoclave (titanium
Various chemical, physical, and electrochemical methods such as, vessel-1 L capacity). The copper solution (500 mL) of known compo-
hydrothermal/solvothermal synthesis, sol–gel, microwave/ultrasound- sition was heated to the desired temperature, and then hydrogen gas
assisted synthesis, thermal decomposition, electrodeposition, and was introduced at a predetermined pressure which was maintained
chemical vapour deposition process, have been applied for the throughout the gaseous reduction. At the end of reduction process,
synthesis of Cu/ZnO nanomaterials (Benhebal et al., 2013; Hu et al., the autoclave was cooled to room temperature. The copper powder
2004; Peulon and Lincot, 1996; Wei et al., 2009; Ni et al., 2005; produced was filtered over a Buchner funnel using Whatman paper
Shah and Al-Ghamdi, 2011; Meshram et al., 2013). Among the (no. 41), washed with distilled water and rinsed with sodium
reported methods, hydrothermal process has been considered as a sim- potassium tartrate solution (2 wt.%) to inhibit the surface oxidation
ple way to synthesize the nano-powders because of the involvement of because the synthesized copper powder is susceptible to oxidation
easy and low-cost procedures, moderate temperature, great control (Bagchi et al., 2012). The copper powder thus obtained was dried in
over experimental parameters and convenience for the synthesis on an oven at 80 °C overnight. Further, the dried powder was annealed in
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 Fig. 1. Effect of pH on the solvent extraction of copper and zinc. Aq. phase: 35 kg/m3 Cu,
the recovery of copper and zinc, sulphuric acid from the pickle liquor 30 kg/m3 Zn, Org. phase: 1 M LIX 984N in kerosene, Phase ratio: 1:1.

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
4 M.K. Sinha et al. / Hydrometallurgy xxx (2015) xxx–xxx

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.
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 3. Results and discussion
the desired temperature for proper granulometry, long term storage
and prevention of oxidation (Bagchi et al., 2012). 3.1. Removal of acid and iron from the pickle liquor
In order to prepare the high purity zinc oxide powder, pH of the
stripped solution containing zinc was increased by adding 1 M NaOH In order to remove/recover acid from the pickle liquor the model
solution dropwise (3 mL/min) with a constant stirring. When the solution containing 35 kg/m3 Cu, 30 kg/m3 Zn , 70 kg/m3 H2SO4, 1.5 kg/m3
desired pH (~12) was reached, the solution (500 mL) was autoclaved Fe (Total), 0.75 kg/m3 Cr and 0.03 kg/m3 Ni was equilibrated with
under the nitrogen atmosphere for 2 h at a pre-set temperature and 40% (v/v) TEHA in kerosene at phase ratio of 2:1. It was observed
pressure. The precipitate of ZnO so obtained was cooled and filtered, that almost total acid was extracted into the organic phase in a single
washed with distilled water and acetone (~50 ml in each experiment); contact. It was also noticed that no copper and zinc was co-extracted
and dried in an oven at 80 °C overnight. into the organic phase which may be due to the less affinity of TEHA
The as-prepared copper metal powder and zinc oxide particles were towards copper and zinc as sulphate. The loaded TEHA was regenerated
characterized by chemical analysis, XRD and SEM-EDS studies. The XRD by stripping with distilled water at 50 °C at a phase ratio (O/A) of unity.
data were recorded (Bruker D8-discover) using CuKα radiation in the It was found that complete H2SO4 were stripped from the loaded TEHA
2θ range of 10–90o. The powder sample was put on a grid and was in 2 contacts. Iron from the acid depleted brass pickle liquor was
coated with gold before recording the SEM (Nova Nano SEM 430). removed by precipitation at pH N3.5. During the precipitation of iron,
co-precipitation of copper and zinc was not observed.

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 Fig. 5. McCabe–Thiele Plot for the extraction of zinc with LIX 984N. Aq. phase: 30 kg/m3 Zn,
Eq. pH = 5.5 for Zn. Org. phase: 1 M LIX 984N in kerosene, 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
 M.K. Sinha et al. / Hydrometallurgy xxx (2015) xxx–xxx 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-
Fig. 6. Counter-current simulation for the extraction of copper with LIX 984N. retical counter-current stages required for complete extraction of
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.
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
3.2. Solvent extraction of copper and zinc with LIX 984N 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
Acid and iron depleted brass pickle liquor contained 35 kg/m3 Cu(II), counter-current extraction of copper or zinc with 1 M LIX 984N
30 kg/m3 Zn(II), 0.75 kg/m3 Cr and 0.03 kg/m3 Ni. In order to establish (Figs. 6 and 7) showed that at the end of the second stage 17.5 kg/m3
the separation of copper and zinc from the above solution, a synthetic copper and at the end of third stage 14.99 kg/m3 zinc were loaded
solution of similar composition (35 kg/m3 Cu(II) and 30 kg/m3 Zn(II)) into the organic phase.
was used to extract Cu/Zn by equilibrating the solution at the desired The above optimized conditions were applied to separate copper
pH with 30% LIX 984N (~1 M) in kerosene as the diluent at the phase and zinc from the spent brass pickle liquor [35 kg/m3 Cu, 30 kg/m3 Zn,
ratio (O/A) of 1:1 and 30 °C for 15 min. Extraction of copper increased 0.75 kg/m3 Cr and 0.03 kg/m3 Ni] in a laboratory scale mixer settler
from 10 to 99% in the equilibrium pH range 1.5 to 3.9 without any unit using 1 M LIX 984N in kerosene as the extractant. Before proceed-
co-extraction of zinc. Extraction of zinc started at equilibrium pH ing for mixer settler operation, sulphuric acid and iron were removed
above 4.5 and increased from 5 to 95% in the equilibrium pH from the pickle solution as described in Section 3.1. The resulting
range 4.8 to 6.4 (Fig. 1). The respective pH1/2 values (pH1/2 = the Fe(OH)3 precipitate can be stored and processed for the production of
pH corresponding to the extraction of 50% of the metal ions into pigment. The flow rates of aqueous and organic phase were maintained
the organic phase) for Cu and Zn were found to be 2.5 and 5.5. Thus according to the requirements of the phase ratio (O/A), which was
it is clear that 1 M LIX 984N is adequate for selective extraction of 2:1 as mentioned above. The pH of the solution in every extraction
copper over zinc with a ΔpH1/2(Zn–Cu) of 3.0, and there is no chance step was maintained to the desired level using required amount of
of mutual contamination of one metal with the other during their dilute NaOH solution. In the case of extraction of Cu(II) the organic
solvent extraction with LIX 984N. and aqueous flow rates were maintained at 8.12 L/h and 4.05 L/h,
The saturation loading capacity of LIX 984N for Cu (at equilibrium respectively at equilibrium pH of 2.5. At the end of the second stage
pH 2.5) and Zn (at equilibrium pH 5.5) was also determined separately 17.5 kg/m3 Cu was loaded into the organic phase with no contamination
by repetitive contact of the same organic phase with the fresh aqueous of Zn, Cr and Ni. Before zinc extraction chromium from the copper free
solution at phase ratio 1 until the metal concentration in the raffinate raffinate was completely removed by precipitation at pH 5.3 using 10%
was the same as that of the aqueous feed. The loading capacity of LIX ammonia solution in the presence of ammonium chloride at room tem-
984N was found to be 34.95 kg/m3 for Cu and 29.70 kg/m3 for Zn after perature (Mahmoud and Barakat, 2001); negligible loss of Zn and Ni
four stages. was observed in to the precipitate. The resulting hydroxide precipitate
Stripping of copper/zinc was carried out using meal saturated/ of chromium can be used as colouring agent/pigment or as catalyst for
loaded LIX 984N containing 34.95 kg/m3 Cu or 29.70 kg/m3 Zn with organic reactions. After chromium removal the solution [30 kg/m3
different concentrations of sulphuric acid (0.25–1.5 M) at O/A Zn(II) and 0.03 kg/m3 Ni] was subjected to solvent extraction of zinc
phase ratio of 1. Stripping of both the metal ions increased with an in the mixer settler unit at the equilibrium pH 5.5 and O/A ratio of
increase in the sulphuric acid concentration (Fig. 2) and with 1.5 M 2:1 (flow rates of organic = 8.12 L/h and aqueous = 4.05 L/h). After
sulphuric acid both the metal ions were stripped quantitatively in a three stages of counter-current extraction 14.99 kg/m3 zinc was loaded
single stage. in to the organic phase leaving nickel in the raffinate.

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
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.

and temperature optimization experiments it was concluded that the
The high loading of copper and zinc in the two streams of the high temperature and hydrogen pressure were preferred and necessary
extractants, is beneficial for the synthesis of the value added products to enhance reduction kinetics. In the beginning, 1 g copper powder was
from the respective stripped solutions of high metal concentration. also added as a seed to accelerate the reaction rate and to avoid copper
The results show that copper and zinc were completely stripped with plating on the stirrer and interior of the reaction vessel (Meshram et al.,
150 kg/m3 sulphuric acid solutions from their respective loaded organic 2013). Copper seed acts as heterogeneous nucleating site for the
phases at O/A ratio of 1:1 in a single stage. nucleation of copper, which have comparatively low energy require-
ment than that of homogeneous nucleation. This enhances the overall
3.4. Synthesis of the value added products reaction rate and prevents copper plating on the vessel. After the exper-
iment the aqueous filtrate was analysed for copper which was found to
3.4.1. Hydrothermal synthesis of copper powder be 0.08 kg/m3; the filtrate can be recycled back to the copper stripping
The purified copper and zinc solutions generated in the processing of circuit. Under the above conditions the recovery of copper as powder
spent brass pickle liquor by solvent extraction with LIX 984N as was found to be 99.5%. The copper powder obtained was filtered,
discussed above, were used for the synthesis of high purity copper washed and dried as mentioned earlier before it was annealed at 500 °C
metal powder and zinc oxide particles. Copper powder was produced in a tubular furnace with a flow of hydrogen gas (5 L/min). The overall re-
by the reduction of Cu2+ ions present in the purified copper sulphate duction of copper sulphate solution to copper powder can be represented
solution under hydrogen atmosphere in an autoclave at 20 bar H2 pres- as (Agrawal et al., 2006a):
sure, 423 K and 400 rpm for 2 h. The hydrothermal reduction of copper
at high temperature and hydrogen pressure from highly acidic copper Cu2þ þH2 →CuHþ þHþ ð1Þ
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 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 ð3Þ The following conclusions have been drawn:

CuH þ Cuþ →2Cu þ Hþ 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 annealed copper powder was characterized by SEM and XRD. • The number of counter-current stages for extraction of copper and
The XRD pattern (Fig. 8) of the copper particles shows the presence of zinc was determined from the McCabe–Thiele plots. Copper was
only copper phase as all the peaks agreed well with the reported data completely extracted in two counter-current stages in a laboratory
for pure copper (JCPDS file No. 04–0836). The sharp diffraction peaks scale mixer settler unit using 1 M LIX 984N at equilibrium pH 2.5
imply that the copper powder has good crystallinity. The purity of the and phase ratio (O/A) 2/1.
synthesized Cu powder (chemical analysis) was found to be 99.9% • Zinc was extracted from the copper free raffinate followed by
with impurity content of 0.015% Zn, 0.018% Fe and 0.005% Ni. The SEM chromium removal, in three counter-current stages using 1 M LIX
image (Fig. 9a) of the synthesized copper powder after annealing 984N at the equilibrium pH 5.5 and phase ratio (O/A) 2/1.
shows that the particle size ranges between 50 and 100 μm with • From the respective metal loaded organics, copper and zinc were
globular shape. High purity of the as-synthesized copper powder is also stripped with 150 kg/m3 H2 SO 4 solutions. The globular shaped
confirmed by the EDS (Fig. 9b). The copper powder has characteristics (50–100 μm size) copper powder of high purity (99.9%) was
suitable for the powder metallurgical (P/M) applications. synthesized from the purified copper solution in an autoclave by
hydrogen reduction at 20 bar pressure (H2), 423 K and 400 rpm.
3.4.2. Hydrothermal synthesis of ZnO powder from the stripped solution • High pure zinc oxide particles of rice grain shape (0.5–1 μm size) were
In order to synthesize the ZnO powder, the pH of the purified synthesized by hydrothermal precipitation at 423 K and pH 12. The
solution containing 14.99 kg/m3 Zn was raised to 12 by slow addition synthesized copper metal powder and zinc oxide particles were
of 1 M NaOH with constant stirring. The highly basic pH was chosen characterized by chemical analysis, XRD and SEM-EDS studies, and
to ensure product purity and faster growth rate of the zinc oxide can be used for various applications.
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, Acknowledgements
washed with distilled water and dried overnight in an electrical oven
at 80 °C. The hydrothermal conversion of zinc sulphate solution to Authors are thankful to the Director of the CSIR-National Metallurgical
ZnO can be expressed as (Aimable et al., 2010): Laboratory (NML), Jamshedpur, India for giving permission to publish the
paper. Thanks are also due to DST, Govt. of India for sponsoring the project
Zn2þ þ4OH‐ →ZnðOHÞ4 2‐ ð5Þ under RFBR (Russia)-DST (India) bilateral programme (Grant no. INT/
RFBR/P-29/2008).
ZnðOHÞ4 2‐ →ZnO þ 2OH‐ þH2 O ð6Þ
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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