Waste Management xxx (2017) xxx–xxx

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Waste Management
journal homepage: www.elsevier.com/locate/wasman

A novel approach for recovery of metals from waste printed circuit

boards and simultaneous removal of iron from steel pickling waste
liquor by two-step hydrometallurgical method
Lili Wang a, Qiao Li a, Yi Li a, Xiuyun Sun a,⇑, Jiansheng Li b, Jinyou Shen b, Weiqing Han b, Lianjun Wang a,b
a
Jiangsu Key Laboratory of Chemical Pollution Control and Resources Reuse, School of Environmental and Biological Engineering, Nanjing University of Science and
Technology, Nanjing 210094, Jiangsu Province, China
b
Engineering Research Center for Chemical Pollution Control (Ministry of Education), School of Environmental and Biological Engineering, Nanjing University of Science and
Technology, Nanjing 210094, Jiangsu Province, China

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

Article history: Waste printed circuit boards (WPCBs) and steel pickling waste liquor (SPWL) have received extensive
Received 19 July 2017 attention in recent years because of its harmfulness and resource. In this work, two-step leaching process
Revised 17 September 2017 was carried out by using SPWL as the leaching agent. A series of continuously domesticated bacteria were
Accepted 3 October 2017
used for bioleaching and the bacterial strain was identified as Acidithiobacillus ferrooxidans (A. ferroox-
Available online xxxx
idans) by 16S rDNA gene sequence analysis. The vast majority of the metals in WPCBs were recovered by
two-step leaching, such as Cu, Pb, Zn, Sn, Al, Ni. Meanwhile, a large amount of iron was removed from
Keywords:
SPWL, which greatly reduces the burden of the subsequent treatment. Pulp density and pH were opti-
Waste printed circuit boards
Steel pickling waste liquor
mized to achieve maximum recovery of copper and simultaneous removal of iron in bioleaching. It
Domesticated bacteria was found that the optimum conditions were pulp density 60 g/L and pH 0.5–1.0. Nearly 100% of copper
Kinetic model was recovered and 51.94% of iron was removed under optimum conditions. The kinetic experiments
Optimization showed that the rate of copper leaching was controlled by external diffusion rather than internal diffu-
sion, because the acidic environment of the leachate prevented the formation of the precipitate and
maintained it in a smaller size.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction are very valuable in recycling (Chen et al., 2015a). The purity and
amount of metals contained in WPCBs are higher than those in
In recent years, the production of electrical and electronic rich-content minerals, which could be considered as an ‘‘Urban
equipments (EEEs) has substantially increased with the develop- Mine”. Therefore, it is of great significance for environmental pro-
ment of science and technology. Printed circuit boards (PCBs) are tection and energy value to seek a scientific and environment-
the basal and essential components of electrical and electronic friendly method to recycle the metals from WPCBs. At present,
equipments (EEEs), widely used in computers, personal computers, the existing methods of recycling metals from WPCBs include
television, mobile phones and other electronic products (Huang mechanical separation, pyrometallurgical, hydrometallurgical and
et al., 2009; Silvas et al., 2015). The current electronic products biohydrometallurgical techniques (Birloaga et al., 2013). Mechani-
are being replaced with faster rate and the lifecycles are getting cal separation is usually used in the pretreatment process to
shorter and shorter. The amount of waste electrical and electronic increase the metal content of WPCBs to be processed, which
equipments (WEEE) is increasing dramatically (Flandinet et al., includes crushing, vibration and electrostatic separation (Zhu
2012). As a result, electronic pollution caused by WPCBs has et al., 2013). Pyrometallurgy requires high investment and pro-
become a serious environmental problem. duces large amounts of toxic and harmful substances, which makes
WPCBs contain polymers, ceramics and metals. The proportion it less applications in the recycling of metals in WPCBs. Hydromet-
is 23%, 49%, 28%. The typical metals, including Cu (20%), Fe (8%), Sn allurgical processes also used to be expensive as it involved long
(4%), Ni (2%), Pb (2%), Zn (1%), Ag(0.2%), Au (0.1%), and Pd (0.005%), procedures, lower efficiency of metal recovery, heavy consumption
of chemicals and secondary pollution. Biohydrometallurgy is the
process of dissolving metal from ore or recovering valuable metals
⇑ Corresponding author. from water, using certain microorganisms or their metabolites on
E-mail address: [email protected] (X. Sun).

https://doi.org/10.1016/j.wasman.2017.10.002
0956-053X/Ó 2017 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Wang, L., et al. A novel approach for recovery of metals from waste printed circuit boards and simultaneous removal of
iron from steel pickling waste liquor by two-step hydrometallurgical method. Waste Management (2017), https://doi.org/10.1016/j.wasman.2017.10.002
2 L. Wang et al. / Waste Management xxx (2017) xxx–xxx

the oxidation, reduction, dissolution and absorption of certain min- 2. Materials and methods
erals and elements. Compared with the traditional metallurgical
technology, biohydrometallurgy has the advantages of low cost, 2.1. Preparation of WPCB sample
low energy consumption, no pollution, simple operation, etc.
(Arshadi and Mousavi, 2015; Bryan et al., 2015; Chi et al., 2011; WPCBs used in this study were obtained from a local e-waste
Yang et al., 2014). The advanced technology of biohydrometallurgy collection center in Nanjing, China. No physical or mechanical sep-
has remarkable economic and environmental benefits, which has aration process was used before transportation to laboratory.
been popularized, perfected and improved in the world. Before the PCBs powder preparation, printed circuit board compo-
At present, the most commonly used microorganisms are A. fer- nents, such as capacitors, resistors, transistors and cables, were
rooxidans in leaching metals contained in WPCBs (Arshadi and manually separated from the PCBs. Then, the PCBs powder samples
Mousavi, 2014). This bacterium is mesophilic, chemolithotrophic, were prepared in three-stage crushing operation. Initially, the PCBs
gram-negative, acidophilic that obtains energy by oxidizing Fe2+ were manually cut into small pieces (diameter <40 mm) using
to Fe3+ and sulfur to sulfate, usually present in acidic environments stainless steel blades. Next, the samples were chopped by a high-
with pH values of 1–3 (Kurade et al., 2016). It was frequently used speed universal pulverizer (FW-400A). Finally, the PCB powders
in biological leaching process of copper. The process of copper dis- were sieved using a vibrator shifter through #16 mesh and dried
solution by bioleaching can be divided into two consecutive peri- in an oven (Wiseven, Won 50) at 105 °C for 2 h, which were
ods. Fe2+ is oxidized to Fe3+ under the action of microorganism, selected and used for all the leaching experiments.
and Fe3+ reacts with copper to make it into the solution. Copper
is leached and Fe3+ is reduced to Fe2+. This cycle is repeated, which 2.2. Microorganisms and domestication conditions
is similar to the indirect mechanism of microbial leaching (Chen
et al., 2015b). Bacterial strain used in this study was A. ferrooxidans ATCC
Numerous studies have shown that WPCBs contain certain 23270. This strain was provided by Jiangsu Key Laboratory of
other active metals (Chen et al., 2015a), which may compete with Chemical Pollution Control and Resources Reuse, School of Envi-
copper leaching, resulting in lower leaching efficiency of copper. ronmental and Biological Engineering, Nanjing University of
Thus, this study intends to adopt chemical-biological two-step Science and Technology, Nanjing, China. The selected strain was
leaching process to recovery metals from WPCBs. The primary cultured in the 9 K medium. The composition was as follows:
chemical leaching was treated with SPWL as leaching agent and (NH4)2SO4 3.00 g/L, KCl 0.10 g/L, K2HPO4 0.50 g/L, MgSO4
7H2O
bioleaching employed A. ferrooxidans as leaching microorganisms. 0.50 g/L, Ca (NO3)2 0.01 g/L, FeSO4
7H2O 44.6 g/L. The pH of med-
SPWL is discharged from steel industry during pickling process, ium was adjusted to 2.0 by 5.0 M sulfuric acid. The culture of A. fer-
which is acidic and contains a mass of Fe2+ (Leonzio, 2016; rooxidans was incubated in 250 mL Erlenmeyer flask containing
Pathak et al., 2016; Rögener et al., 2012). The composition of the 200 mL of the medium and 10% (v/v) inoculums, on a rotary shaker
SPWL used in this study is shown in Table 1. Then, the leaching at 180 rpm and 30 °C (Ma et al., 2017; Rastegar et al., 2015; Yan
technology takes full advantage of Fe2+ of SPWL used as the energy et al., 2016). Culture conditions for further experiment were the
source of the microorganism in the bioleaching, which avoids the same as described here. The series of domestication was carried
addition of the bioleaching iron source and greatly saves the leach- out to obtain the bacteria required for bioleaching by successive
ing cost. Simultaneously, the great majority of the iron in SPWL is transfer method, including resistance to chlorine, SPWL, and
removed in the form of iron precipitate, which greatly reduces the WPCBs. The results suggested that the highest tolerance of bacteria
burden of iron removal of SPWL. More importantly, the iron pre- to WPCBs was 60 g/L and the time required for bacteria to adapt
cipitate by drying treatment can also be used for concrete admix- was 7 d, which is far superior to the previous reported results
ture, catalyst, absorbent agent, etc. (Chen et al., 2017; Li et al., (Arshadi and Mousavi, 2014, 2015).
2015; Sheydaei and Khataee, 2015; Wang et al., 2017; Zheng
et al., 2016), so as to realize the reutilization of waste. In this study,
the chemical leaching reduce the pressure of subsequent bioleach- 2.3. Molecular analysis of domesticated bacteria NJLGS18
ing after the preliminary leaching of copper in WPCBs, which
makes the overall leaching cycle greatly shortened. To sum up, The bacterial community after domestication was identified
using 16S rDNA sequencing and phylogenetic analysis according
the application of SPWL makes the whole leaching process more
economical, significant savings in leaching costs, while the SPWL to previous study. For the DNA analysis, the domesticated bacteria
has been a large degree of treatment. were centrifuged for 5 min at 8000 rpm (Huang et al., 2016). Then
the DNA was extracted using the FastDNA SPIN kit according to the
The present study aims to realize the resource utilization of
waste. On the one hand, the metal in the WPCBs is recovered. On manufacturer’s instructions (MP Bio-medicals, CA, USA). The DNA
samples were stored at 20 °C until further analysis (Jiang et al.,
the other hand, the iron in SPWL is removed, and the generated
iron precipitate is further utilized. Taking into account the operat- 2016). The extracted DNA was used as template of polymerase
chain reaction (PCR) to amplify 16S rDNA using the universal pri-
ing environment of this experiment, a strain resistant to WPCBs
and SPWL was domesticated and its genes were identified. Simul- mers 27F (50 -AGAGTTTGATCCTGGCTCAG-30 ) and 1492R (50 -GGTT
ACCTTGTTACGACTT-30 ) (Patel et al., 2011). The PCR amplification
taneously, the leaching parameters were optimized and the kinet-
ics of the bioleaching process were analyzed to improve program was carried out at an initial denaturation at 95 °C for 5
min, and 30 cycles at 95 °C for 30 s, 55 °C for 30 s, 72 °C for 120 s
bioleaching performance. It is proved to be an effective method
for recovery of metals from WPCBs and simultaneous removal of and a final extension at 72 °C for 2 min. The quality of the ampli-
fied DNA was confirmed through 1.5% agarose gel electrophoresis.
iron from SPWL.
Then the PCR product was purified using a QIAquick-spin PCR

Table 1
Chemical analysis of SPWL.

Composition Total Fe Fe2+ Fe3+ Zn Al Pb Cu H+ Cl

Concentration/(g/L) 173.11 165.77 7.34 1.84 0.07 0.01 0.04 0.66 252.59

Please cite this article in press as: Wang, L., et al. A novel approach for recovery of metals from waste printed circuit boards and simultaneous removal of
iron from steel pickling waste liquor by two-step hydrometallurgical method. Waste Management (2017), https://doi.org/10.1016/j.wasman.2017.10.002
 L. Wang et al. / Waste Management xxx (2017) xxx–xxx 3

purification kit (Qiagen, Hilden, Germany) (Dave et al., 2008). Optical Emission Spectrometer (ICP-OES) (Optima 7000DV, Perki-
Eventually, DNA sequencing was conducted by DNA sequencer nElmer, USA). The pH values were analyzed by the pH analyzer
(ABI3730XL) and BLAST analysis was executed in GenBank (Mettler FE20, Mettler Toledo, USA).
(http://www.ncbi.nlm.nih.gov/blast/). On the basis of homology
comparison of the domesticated bacteria, a phylogenetic tree of 3. Results and discussions
the 16S rDNA genes was generated using a MEGA 6.06 (Qiu et al.,
2011). 3.1. Characterization of WPCBs samples

2.4. Leaching experiments The WPCBs samples were analyzed under X-ray diffraction
(XRD) and the presence of Sn, Cu, Al, Zn, Fe3O4, PbO and SiO2
In this work, heavy metals in WPCBs were leached using a was determined. The metal content in WPCBs samples was analyze
chemical-biological two-step leaching process. All experiments using Electric Heating Plate Digestion with HNO3-HClO4-HF (2: 1:
were carried out in 250 mL Erlenmeyer flask. The chemical leach- 1, v/v) (Labtech, EH-35B). The average content of Cu, Zn, Pb, Al,
ing reaction system adopts SPWL as the leaching agent. The opti- Fe, Sn, Ni, Mg, Mn, Ag and Sb is given in Table 2. In order to deter-
mization conditions of chemical leaching were determined by mine the leachability of toxic metals from WPCBs, the Toxicity
response surface methodology and kinetic analysis. The effects of Characteristic Leaching Procedure (TCLP) method was selected
rotating speed, temperature, dosage and particle size on copper (USEPA, 1992). As can be seen from Fig. 1(a), Cu, Pb, Ba, Cr, As
leaching were determined. The results showed that the optimum can be detected, especially Cu. The TCLP-Cu concentration in the
leaching condition were rotational speed 600 rpm, temperature WPCBs was 2.79 times higher than the USEPA regulatory level of
45 °C, dosage 60 g/L and particle size 1.00 mm. The subsequent 15 mg/L, indicating that WPCBs possessed serious environmental
bioleaching experiments were carried out under the optimum con- hazards. The particle size distribution is presented in Fig. 1(b). Rep-
ditions of chemical leaching. A majority of the active metals have resentative diameters for the particle sets are shown in Table 3.
been leached in the chemical leaching process, such as Pb, Zn, Sn, The results indicate that the WPCBs powder particles are finer,
Al. Meanwhile, copper as the major metal of WPCBs (Table 2) mainly concentrated in the range of 10–1500 lm, while the WPCBs
was partially leached in the above leaching process. The results particle size distribution is not uniform. Fig. 1(c) shows the SEM
showed that chemical leaching can reach equilibrium state at 48 images of WPCBs powder. As can be seen from the figure, the
h, followed by bioleaching. Bioleaching was carried out by shaking WPCBs powder is mainly rod-shaped and has many fine particles
flask experiments on a rotary shaker at 180 rpm and 30 °C. The vol- attached to it.
ume loss of the experiment due to evaporation was supplemented
by adding an equal amount of deionized water through the scrib- 3.2. Identification of domesticated bacteria NJLGS18
ing method. The domesticated bacteria NJLGS18 was used for all
bioleaching experiments and its growth conditions are as After a series of domestication, A. ferrooxidans NJLGS18
described above. involved a certain degree of evolution, which improved toxic toler-
In order to optimize the bioleaching process, the influence of ance of bacteria. The electrophoretic analysis (Fig. 2(a)) revealed
initial pH and pulp density were investigated experimentally. A that the PCR products of NJLGS18 showed specific amplification
series of flasks were arranged with the initial pH at 0.5, 1.0, 1.5, of a single band 1.5 kb of 16S rDNA, indicating the primers for
2.0 and 3.0, various amounts of pulp density at 20 g/L, 60 g/L, NJLGS18 have the high specificity (Xu et al., 2014).
100 g/L. The copper leaching rate and iron removal rate were mea- The nucleotide sequence of 16S rDNA was analyzed by BLAST to
sured in the cultivation process to determine the optimum condi- seek the closest related species with the bacterial strains in the
tions. Simultaneously, the kinetic experiments were conducted by GenBank database. It was found that the similarity about some
analyzing the concentration of Cu2+, Fe2+, Fe3+, pH and the redox strains of A. ferrooxidans with domesticated bacteria NJLGS18
potential. When the bioleaching was completed, all the precipi- was greater than 99% after BLAST comparison in the sequence
tates were dried and sealed for subsequent application analysis. database. A phylogenetic tree of the 16S rDNA gene sequences of
Each experiment was carried out triplicate and the average was NJLGS18 and reference phylogenetic analysis is presented in
reported. Fig. 2(b). It can be seen from the figure that the domesticated bac-
teria had a good homology with the strains of A. ferrooxidans, indi-
2.5. Analytical methods and instruments cating that they have a close relationship with each other (Xu et al.,
2014; Yan et al., 2017). Further analysis showed that the strain
The metal content of the sample was determined by using hot NJLGS18 was most closely related to A. ferrooxidans strain Tz
aqua regia digestion. With regard to analysis of samples before (KM 819691) with 99% similarity (Chen et al., 2009; Li et al.,
and after leaching, the mineralogical compositions were deter- 2013; Ouyang et al., 2013). The nucleotide sequence was submit-
mined by X-ray diffraction (XRD) (D8 Advance, Bruker, Germany) ted to GenBank as A. ferrooxidans with the accession number
with Cu K a radiation (40 kV and 40 mA) and the morphology KT203930.
was observed by scanning electronic microscope coupled with
energy dispersive spectroscopy (SEM-EDS) (Quanta 250FEG, FEI, 3.3. Optimization experiment of bioleaching conditions
USA). Fe2+ concentration was measured by o-phenanthroline
method at the absorption wavelength of 510 nm (UV759, SPS) 3.3.1. Effect of the pulp density
(Xiang et al., 2010). In addition to Fe2+, the metal concentrations The main purpose of bioleaching is further leaching of copper in
in the experiment were measured by Inductively Coupled Plasma WPCBs, as well as the precipitation of iron in SPWL. The pulp den-

Table 2
The metal content of the WPCB sample.

Elements Cu Zn Pb Al Fe Sn Ni Mg Mn Ag Sb
Content (%) 24.97 3.52 2.60 2.32 1.89 1.03 0.26 0.13 0.016 0.007 0.002

Please cite this article in press as: Wang, L., et al. A novel approach for recovery of metals from waste printed circuit boards and simultaneous removal of
iron from steel pickling waste liquor by two-step hydrometallurgical method. Waste Management (2017), https://doi.org/10.1016/j.wasman.2017.10.002
4 L. Wang et al. / Waste Management xxx (2017) xxx–xxx

(a) (b)

(c)

Fig. 1. Characterization of WPCBs samples. (a): Toxicity characteristics leaching procedure (TCLP) extracted various metals in WPCBs; (b): cumulative particle size
distribution for the particle sets considered in this paper; (c): SEM images of WPCBs powder used in this paper.

Table 3 sity is a critical factor affecting the process and its concentration is
Particle size for the WPCBs powder used in this paper. controlled at 20 g/L, 60 g/L and 100 g/L, respectively.
Characteristic diameter d10 d50 d90 The copper leaching rate and the iron removal rate after
Particle size (lm) 14.0 199.0 906.0 bioleaching 10 d and 15 d was measured and the results were
shown in Fig. 3. It was indicated that the bioleaching efficiency

Fig. 2. Genomic DNA analysis and phylogeny of domesticated bacteria NJLGS18. (a): 16S rDNA fragments amplified from the genomic DNA isolated from its pure cultures
(Lane 1, 2: NJLGS18 and lane X: 10 kb DNA ladder); (b): phylogenetic tree derived from the 16S rDNA gene sequence of the bacteria NJLGS18.

Please cite this article in press as: Wang, L., et al. A novel approach for recovery of metals from waste printed circuit boards and simultaneous removal of
iron from steel pickling waste liquor by two-step hydrometallurgical method. Waste Management (2017), https://doi.org/10.1016/j.wasman.2017.10.002
 L. Wang et al. / Waste Management xxx (2017) xxx–xxx 5

Fig. 3. Effect of the pulp density on bioleaching. (a): Copper leaching rate; (b): iron removal rate.

decreased rapidly as the WPCBs increased from 20 g/L to 100 g/L. 3.3.2. Effect of initial pH
The similar conclusion has been reported (Wang et al., 2009). After chemical leaching, the pH of SPWL was still undetectable
When the pulp density increases, the toxicity of microorganisms by the pH analyzer, because of strong acidity of SPWL. It is neces-
increased, so that its activity decreased, which is a major factor sary to adjust the pH of the solution to investigate its influence on
in inhibiting copper leaching. Another important factor affecting the leaching of copper. That is mainly reflected in two aspects. On
copper leaching is the formation of iron precipitates. The growth the one hand, pH has a significant effect on the activity of the bac-
of microorganisms consumes a large amount of H+ (Eq. (1)), which teria (Yang et al., 2009). On the other hand, pH affects obviously
promotes the hydrolysis of Fe3+ (Eq. (2)), thereby increasing the the Fe3+ concentration due to the generation of iron precipitates.
generation of iron precipitates (Wang et al., 2009). Therefore, when As shown in Fig. 4, the leaching rate showed a trend, which
the pulp concentration is low, the growth of microorganism is bet- increased first, then decreased, and finally increased slowly. A
ter, which will increase the leaching rate of copper and produce slight decrease in the leaching rate of copper is mainly due to
more iron precipitates. However, Fig. 3(a) shows that the copper the role of iron precipitates adsorption mentioned above. At the
leaching rate decreases by 10 d compared to 15 d at pulp density end of 50 d, regardless of the initial pH, copper can be leached
20 g/L, which may be caused by the adsorption of iron precipitates completely. When pH is elevated, it is not conducive to the growth
(Mohamed et al., 2017; Yang et al., 2009). It is clear that the of bacteria, because the bacteria used in this study have been
adsorption has little effect on high pulp density. domesticated by SPWL, which is reflected in the leaching rate of
copper (Fig. 4(a). While the increase of initial pH value promotes
A:ferrooxidans the formation of iron precipitates (Fig. 4(b)). Therefore, the goal
4Fe2þ þ O2 þ 4Hþ ! 4Fe3þ þ 2H2 O ð1Þ of simultaneous leaching of copper and iron removal is conflicting.
Bioleaching at 8 d is the key point of leaching, where the copper
leaching rate reaches its maximum at stage leaching. Especially at
Fe3þ þ 3H2 O $ FeðOHÞ3 þ 3Hþ ð2Þ
initial pH 0.5, the copper leaching rate can even reach 93.7% with
Accordingly, 60 g/L was selected as the optimum pulp density in the iron removal rate of 23.2%. When initial pH increased to 3.0
the following experiments. (Fig. 4), the copper leaching rate decreased to about 31.77% with

Fig. 4. Effect of pH on bioleaching. (a): Copper leaching rate; (b): iron removal rate. When different pH values were adjusted, the experimental error was controlled within
±0.05.

Please cite this article in press as: Wang, L., et al. A novel approach for recovery of metals from waste printed circuit boards and simultaneous removal of
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6 L. Wang et al. / Waste Management xxx (2017) xxx–xxx

the outside of the liquid boundary layer; (2) the liquid reactant
or product is diffused through the solid product layer; (3) interface
chemical reaction. Previous studies have shown that metal dissolu-
tion can be described by shrinking core model theory of the liquid-
solid phase reaction (Eq. (3)), where the reaction rate is controlled
by a solid product layer diffusion. When the reaction is controlled
by a chemical reaction, the leaching kinetics process can be repre-
sented by Eq. (4). If no product layer is formed during the reaction,
the reaction particles will gradually decrease until it disappears.
For small particles, this can be explained by a Stokes regime (Eq.
(5)) and the reaction rate is controlled by the liquid boundary layer
diffusion (Mishra et al., 2008).

kt ¼ 1  2=3x  ð1  xÞ2=3 ð3Þ

kt ¼ 1  ð1  xÞ1=3 ð4Þ

kt ¼ 1  ð1  xÞ2=3 ð5Þ
Fig. 5. The bioleaching kinetics of the copper leaching. (A: The rate control by
chemical reaction of leaching. B: The Stokes regime model. C: The shrinking core where x represents the leaching rate, t represents the react time, k
model.) represents the rate constant, respectively.
The data of copper leaching rate versus time at pH 0.5 is shown
Table 4 in Fig. 4(a). As can be seen from the figure, copper leaching rate
Lines of best-fit equations and correlation factors for various kinetic leaching models. increased in the first 8 d, then decreased, finally increased slowly.
This result has been explained in Section 3.2. Considering that the
Kinetic model Fitted Curves Correlation factor
kinetic analysis is mainly the study of copper leaching, this study
Chemical reaction controlled Y = 0.0634x + 0.1591 R2 = 0.9356
adopts the leaching data of first 8 d for dynamic fitting, which is
The Stokes regime model Y = 0.0705x + 0.3446 R2 = 0.9864
The shrinking core model Y = 0.0288x + 0.0115 R2 = 0.9266
depicted in Fig. 5. The fitting results of each kinetic model are
shown in Table 4. It is shown that the Stokes regime model is more
suitable than the others and the correlation coefficient reached
0.9864. It can be seen that the liquid boundary layer diffusion is
the iron removal rate of 24.0%. This result is primarily in consider-
the controlling step of the bioleaching. This result indicates that
ation of the decrease of Fe3+ concentration.
the precipitate formed during the bioleaching process does not
In summary, taking into account the ultimate goal, the maxi-
adhere to the surface of the particles, so that the precipitate does
mum both copper leaching rate and iron removal rate, this study
not prevent the transfer between the liquid and solid phases. It is
should adjust the initial pH between 0.5 and 1.0.
presumed that this result is attributed to strong vibrations of the
shaker and the contribution of the acid (Chen et al., 2015b).
3.4. Kinetics of copper leaching Fig. 6 shows the growth characteristics of domesticated bacteria
versus time under optimal conditions for 28 d. As can be seen from
Bioleaching kinetics is critical to analyze the mechanism of cop- the result, the pH increased significantly in the initial stage of
per leaching from WPCBs. The kinetic analysis can determine the bioleaching as a result of the H+ consumption during microbial
rate controlling step to maximize the efficiency of the reaction. growth. Then the microbial growth tended to be stable (Fig. 6(a))
The leaching reaction of solid product formation is also a very com- and pH decreased gradually due to the hydrolysis of Fe3+ (Eq.
mon reaction in hydrometallurgy, which consists of the following (2)). As shown in Fig. 6(b), Fe2+ is constantly oxidized to Fe3+,
reaction steps: (1) liquid reactants or products diffuse through thereby reducing Fe2+ concentration. However, the Fe3+ concentra-

Fig. 6. Changes of growth parameters during bioleaching experiments. (a): pH and redox potential; (b): Fe2+ and Fe3+ concentrations, cell number. (The experiment was
carried out under optimum condition at pulp density 60 g/L and pH 0.5.)

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 L. Wang et al. / Waste Management xxx (2017) xxx–xxx 7

Fig. 7. The XRD patterns of precipitates after bioleaching for 50 d. (a) Comparison of the XRD patterns of the blank group and the initial pH at 0.5, 1.0, 1.5, 2.0, 3.0,
respectively; (b) Analysis of XRD patterns at pH 3.0.

Fig. 8. SEM images of precipitates after bioleaching for 50 d. ((a–f) Represent the blank group and the initial pH at 0.5, 1.0, 1.5, 2.0, 3.0, respectively.)

tion did not rise, which also confirmed the conclusion of iron pre- cipitate morphology under the different pH, basically no difference.
cipitation. The low pH in the bioleaching process maintains the Therefore, pH does not affect the composition and morphology of
precipitate at a small size, which does not affect the leaching of the precipitates.
copper. Hence, the bioleaching process of copper is controlled by After the previous two steps of leaching, almost all of the metal
the liquid boundary layer diffusion rather than the solid product has been leached. Fig. 8 indicates that the presence of leaching resi-
layer diffusion. due had not been observed. The structure of precipitates is rather
loose, and its size is less than 5 lm, which makes it have a slight
effect on bioleaching. This result just explains why the bioleaching
3.5. Analysis of bioleaching precipitation process of copper is controlled by the liquid boundary layer diffu-
sion rather than the solid product layer diffusion (Chen et al.,
3.5.1. Characterization 2015b).
In order to investigate the effect of pH on the formation of pre-
cipitates, the relevant XRD and SEM were analyzed. As shown in
Fig. 7(a), the peak positions of the XRD patterns under different 3.5.2. Applications
pH are completely identical and the basic composition is FeOOH A large amount of precipitates is produced after bioleaching,
and Fe3O4 (Fig. 7(b)), which confirms that pH has no effect on the which results from the high content of iron in the SPWL, as shown
composition of the precipitates. Meanwhile, Fig. 8 shows the pre- in Table 2. Therefore, it is of great significance to carry out the sub-

Please cite this article in press as: Wang, L., et al. A novel approach for recovery of metals from waste printed circuit boards and simultaneous removal of
iron from steel pickling waste liquor by two-step hydrometallurgical method. Waste Management (2017), https://doi.org/10.1016/j.wasman.2017.10.002
8 L. Wang et al. / Waste Management xxx (2017) xxx–xxx

Based on the leachability of toxic metals from precipitates, the

Toxicity Characteristic Leaching Procedure (TCLP) method was
adopted (Yan et al., 2015). As shown in Fig. 9, the results demon-
strated that the concentration of copper 16.06 mg/L in leachates
was slightly higher than the USEPA regulatory levels 15 mg/L,
which indicates that the application of precipitation has an impact
on the environment (USEPA, 1992). The reason for the above
results is attributed to the adsorption of iron precipitates, which
greatly limits its subsequent application. How to reduce the toxic-
ity of precipitation is an important issue in subsequent study,
which is of great significance for the recovery of iron in SPWL.

4. Conclusions

The thought, the SPWL is introduced into the metal leaching of

WPCBs, takes full advantage of the characteristics of two wastes. It
is proved to be an effective method for recovery of metals from
WPCBs and simultaneous removal of iron from SPWL. After contin-
Fig. 9. Toxicity characteristics leaching procedure (TCLP) extracted various metals uous domestication experiments, the bacteria resistant to WPCBs
in iron precipitates. In the figure, ND represents Not Detected.
and SPWL were domesticated and the highest tolerance of WPCBs
can reach 60 g/L, which is far beyond the other literature reported.
sequent application of precipitates. In view of the presence of The experimental studies revealed that the optimal operating con-
FeOOH and Fe3O4, it can be used as catalysts, adsorbents, etc ditions for bioleaching were ensured at the pulp concentration 60
(Chen et al., 2017; Li et al., 2015; Sheydaei and Khataee, 2015; g/L and initial pH 0.5–1.0. The kinetic analysis showed that the liq-
Wang et al., 2017; Zheng et al., 2016). However, it is necessary to uid boundary layer diffusion is the controlling step of the bioleach-
analyze its hazardous nature before application. ing. The vast majority of the metals in WPCBs were recovered by

WPCBs,
Disassembly: Electronic components and
Depopulated PCBs

Crushing
(90% of particles < 1 mm)

Chemical Leaching, steel pickling waste liquor as

leaching agent, Fe3+ - 7 g/L, Fe2+ - 166 g/L, H+ - 0.66 M,
pulp concentration - 60 g/L, T = 45 °C, t = 120 h, Stirring
Speed = 600 rpm

Leaching Solution, Cu2+ (6.65 g/L), Zn2+ (2.26 g/L), Pb2+

(1.36 g/L), Fetotal (175 g/L), pH: not detected

Iron precipitation,
Bioleaching, A. ferrooxidans as leaching microorganisms, 10% Applications: catalyst and
(v/v) inoculums, T = 30 °C, t = 8 d, Stirring Speed = 180 rpm adsorbent, concrete
admixtures, etc

Leaching Solution, Cu2+ (11.17 g/L), Zn2+ (2.05 g/L), Pb2+ zinc, lead and tin have
(1.24 g/L), Fetotal (149 g/L), pH = 1.1 been further recovered

Solvent extraction – Stripping - Electrowinning

Pure copper

Fig. 10. Process flow-sheet for recovery of copper by two-step hydrometallurgical method.

Please cite this article in press as: Wang, L., et al. A novel approach for recovery of metals from waste printed circuit boards and simultaneous removal of
iron from steel pickling waste liquor by two-step hydrometallurgical method. Waste Management (2017), https://doi.org/10.1016/j.wasman.2017.10.002
 L. Wang et al. / Waste Management xxx (2017) xxx–xxx 9

two-step leaching, and bioleaching generated large amounts of Leonzio, G., 2016. Recovery of metal sulphates and hydrochloric acid from spent
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by pH. The basic components of precipitate are Fe3O4 and FeOOH, Acidithiobacillus ferrooxidans. Int. Biodeter. Biodegr. 85, 156–165.
which can be widely used in all aspects of industry. After two steps Li, X., Huang, Y., Li, C., Shen, J., Deng, Y., 2015. Degradation of pCNB by Fenton like
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zinc, lead and tin. The process flow for the recovery of copper is Mishra, D., Kim, D.J., Ralph, D.E., Ahn, J.G., Rhee, Y.H., 2008. Bioleaching of spent
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kinetics adsorption data. J. Water Process Eng. 16, 212–222.
Ouyang, J., Guo, W., Li, B., Gu, L., Zhang, H., Chen, X., 2013. Proteomic analysis of
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damental Research Funds for the Central Universities polymetallic concentrate leaching studies of tryptic soy- and peptone-resistant
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Please cite this article in press as: Wang, L., et al. A novel approach for recovery of metals from waste printed circuit boards and simultaneous removal of
iron from steel pickling waste liquor by two-step hydrometallurgical method. Waste Management (2017), https://doi.org/10.1016/j.wasman.2017.10.002