Proceedings of the International Conference on Sustainable Solid Waste Management,

5 - 7 September 2007, Chennai, India. pp.155-162

155
Experimental Study on Metal Recycling from Waste PCB
Gongming Zhou
1
, Zhihua Luo
1
and Xulu Zhai
2

1
National Engineering Research Center for Urban Pollution Control
2
Thermal & Environmental Engineering Institute
Tongji University, Shanghai, China
Email: zhougm@mail.tongji.edu.cn
ABSTRACT
In this paper the method of pyrometallurgy is adopted to recycle metals from waste printed
circuit board (PCB). An experimental stove was build up to smelt PCB to recover its copper
and precious metals. Experimental results showed that NaOH can be used as slag-formation
material to separate metal from slag during pyrolysis process and helped to decrease melting
temperature of waste PCB. Addition of NaOH by 12%wt of PCB helps to recover more than
99% of copper under 1200. At the same time organic substances produced from pyrlysis
process were analyzed and gaseous pollutants especially gaseous bromine pollutants
concentration was quantified. In order to purify the recovered Cu and recovery the noble
silver, the slag and metal obtained in the pyrolysis step were submitted to a smelting step with
air as oxidizing reagent under 1200; the slag addition helped the separation of metal from
the container and improved the silver recovery efficiency. Finally the slag from the smelting
step was used to clean the pyrolysis gas and it was found gas pollutants can be controlled
successfully while part of Cu
2
O is reduced to Cu by the pyrolysis gas to recover Cu. Those
results helped to find a way to recover metals and precious metals from PCB.
Keywords: Printed Circuit Boards (PCB), Pyrometallurgy, Pyrolysis, Silver recovery
1.0 INTRODUCTION
International transfer and consumption concept change in current era of China resulted in a high speed
generation of electronic wastes (E-wastes), and pollution caused by E-wastes is serious. While at the
same time E-wastes are also a special kind of resource, for example a typical E-waste printed circuit
boards (PCB) usually contain epoxy resin, fiberglass, copper, nickel, iron, aluminum and a certain
amount of precious metals such as gold and silver; those materials and metals along with electronic
parts, are attached to the board by a solder containing lead and tin. The lead in the solder and the
bromine fire retardant in the resin must be treated properly during PCB disposal process to prevent
pollution. In order to recover valuable materials and to minimize the adverse effects of hazardous
materials contained in PCB, technologies such as copper-smelting method (Bernardes Andrea;
Bohlinger Isrun; and Rodriguez Diosnel etc.1997), physical separation method (ZHAO Yuemin,
WEN Xuefeng, SHI Hongxia, et al., 2006), scraping method (Mecucci Andrea; Scott Keith, 2002)
have been tried and practiced. During the smelting process, the epoxy resin can be incinerated, and the
fiberglass can be melted into slag. Thus, the smelting process can not only recover the valuable metals
but also properly dispose of the non-recyclable materials in the PCB. But the pollutants produced
Experimental Study on Metal Recycling from Waste PCB
156
during smelting process are a traditional problem; especially the gas emitted pollutants. The physical
separation plant consists of a series of physical treatment units devoted to processes such as crushing,
grinding, screening, magnetic separation, air classification, eddy-current separation, electrical-
conductivity separation, etc. The non-recyclable material (i.e., epoxy resin and fiber glass) is then
separated from the valuable metals. After separation, the purity of recycled materials is not high and
there are still metals in non-recyclable part (Jirang Cui, Forssberg E., 2003). Since no water or
chemical additive is associated with this method, there is no waste water problem in this type of
operation. However, special attention should be given to dust emission and noise-control problems.
The principle of scraping method is to melt the solder on the PCB. After solder is heated to a liquid
state, mounted electronic parts can be mechanically scraped off; then, clean board and scraped-off
parts can be processed separately. The merits of this method is recycling efficiency of PCB can be
increased, due to separate processing of clean board and scraped-off electronic parts. But economic
efficiency is not well established due to the scarcity of full investigation and practice. Also the market
of clean board is not positive as expected since many testing steps are necessary which makes the
recycled ones could be more expensive than new products. In this work an innovated smelting process
is proposed to recover copper and precious metals with gas pollutants cleaned at the same time, and no
waste water is produced in this recovery process.
2.0 INNOVATED PYROMETALLURGY FOR PCB DISPOSAL AND METAL RECOVERY
The process for PCB disposal and metal recovery is shown in Figure 1. In the system the PCBs are
first pyrolysed under reductive atmosphere to let the epoxy resin decompose and separate metals from
slag; then the metals and part of slag are melted under oxidizing atmosphere to melt and purify copper
and recover precious metal simultaneously; and finally the pyrolysis gas containing pollutants in the
first step was cleaned with the melting slag formed in the second step while at the same time part of
Cu
2
O in the slag can be reduced to elemental copper and recovered.

Figure 1 Innovated Pyrometallurgy Technology for PCB Disposal
2.0 MATERIAL AND METHODS
2.1 Material
The PCB used in this research is sampled from waste personal computers. Their elemental analysis is
shown in Table 1.
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157
Table 1. Elemental Analysis of PCB in the Experiments (wt %)
Element Al Ca Fe Mn Pb Sn Ti Ag
content 1.59 3.20 0.22 0.012 0.63 2.31 0.09 0.0242
Element Pt As Cr K Na S Sr Zr
content <0.0027 0.006 0.025 0.027 0.002 0.11 0.02 0.016
Element Au Ba Cu Mg Ni Sb Zn Pd
content 0.0076 0.16 24.69 0.096 0.11 1.97 0.08 <0.0027
2.2 Experimental Setup
The experimental set-up is shown in Figure 2. The size of crucible used in experimental set-up is
60100. In the experiment, firstly the PCB was pyrolysed under 1200 with NaOH added to help
molten of non-metal slag, this step is performed for the purpose of metal separation; Then the
separated metal is molten in air to improve the purity of metal and impurities are concentrated in
Cu
2
O - contained slag. At the same time the gas produced in the first step can be cleaned in this step.

Figure 2 Layout of the Experimental Equipment
1. The upper feeding-in pipe; 2.Cover; 3.Insulating cover; 4.Bolts; 5.Corundum pipe; 6. Corundum
crucible; 7.Water- cooling sheath; 8.The lower gas-in pipe; 9.The lower gas-in valve; 10.Flue gas
pipe; 11.Gas smoke pipe valve
2.2.1 Metal Separation
In this step the waste PCB and the slag- formation material NaOH are heated together to separate
metals. Addition of NaOH is to decrease the melting temperature. Figure 3 shows under lower
temperatures; if more NaOH added, melting of waste PCB can also be happened. As NaOH added by
Experimental Study on Metal Recycling from Waste PCB
158
12wt% of waste PCB the mixture can be melted when heated to 1200 and the epoxy resin is broken
down to reductive gas. In this reductive atmosphere, the metal such as Fe, Cu, Pb and precious metals
will exist in the bottom of the crucible in elemental state; and the slag floating on the top mainly
consists of SiO
2
, Al
2
O
3
, and CaO. After cool down, the metals on the bottom can be easily peeled off
from slag. Figure 4 shows the slag after metal separated. The components of produced gas, slag and
metal are analyzed and the results are shown in Figure 5, Figure 6, Table 2, Table 3 and Table 4.
10
12
14
16
18
20
1080 1120 1160 1200
Melt ing t emperat ure()
R
a
t
i
o

o
f

N
a
O
H

t
o

P
C
B
(
%
)


Figure 3 Influence of NaOH Addition on Melting
Temperature
Figure 4 Molten PCB with Metal Separated and
Slag Left


Figure 5 GCMS Chart of Pyrolysis Gas of Waste
PCB Pyrolysed under 1200 with Addition of
NaOH by 12% under Argon
Figure 6 GC-MS Chart of Oily Material from
Waste PCB Pyrolysis under 1200 with Addition
of NaOH by 12% under Argon
From Table 1 it can be seen that noble metal in personal computer PCB is mainly silver (Ag), other
nobles metals like Au, Pt and Pd are very few, especially Pt and Pd were below the detection limits.
From mass balance calculation based on data in Table 2 and table 3 it was found that the mass ratio of
Cu, Au, and Ag in the metal phase are 99.04%, 94.9% and 99.8% respectively.
From Figure 5, Figure 6 and Table 4 it can be seen that the components of pyolysis gas are mainly
benzene, 2-butyne and toluene. But 1-Butene, 4-bromo-; Butane,1-bromo-; and bromo benzene also
appears from 0.02% to 0.06%. While in Table 4 it can be seen that although Benzene, toluene,
styrene, phenol, benzonitrile, naphthalene, phenol,4-(1-methylethyl)- are the main components in the
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159
pyrolysis oil, the assumed dioxin precursors such as Dibenzofuran, Dibenzofuran,4-methyl-,
Benzo[k]fluoranthene also exist in high concentration. The ultimate analysis of the pyrolysis oil
shows its elemental composition is as follows: C 85.0wt%, H 6.7%wt, O 6.8%wt, N 1.3%wt, Br
0.2%wt, so it is a highly energy-contained material and can by recycled as raw material in chemical
industry but measures should be taken to separate Br from the oil before utilization.
Table 2. Composition of Slag Phase (wt%)
Element Al Ca Fe Mn Pb Sn Ti
content 4.14 8.30 0.18 0.011 0.007 0.024 0.24
Element Pt Pd Ag K Zr S Sr
content <0.004 <0.004 <0.0006 0.070 0.041 0.21 0.053
Element Au Ba Cu Mg Ni Sb Zn
content <0.001 0.42 0.15 0.25 0.002 0.037 0.049
Table 3. Composition of Metal Phase (wt%)
Element Al Ca Fe Mn Pb Sn Ti
content 4.14 0.006 0.49 0.026 2.08 7.71 0.24
Element Pt Pd Ag Si Zn S Na
content <0.004 <0.004 0.080 0.006 0.22 0.11 0.008
Element Au Cr Cu As Ni Sb
content <0.024 0.083 82.247 0.02 0.35 6.54

2.2.2 Oxidization of Cu and Enrichment of Noble Metal
From Table 3 it can be seen that purity of Cu in metal phase is not high enough, there are lot of
impurities in it. So this step is designed to separate Cu from other cheap metals and increase the purity
of Cu. Also it was expected that noble metals go to the metal phase to the greatest extent. For this
purpose, the metal part from the pyrolysis step was smelted and oxidized in air with and without slag
addition. The re-smelted metal without slag is shown in Figure 7; it can be seen part of the Cu
oxidized to Cu
2
O; the Cu
2
O together with other impurities formed the slag on the upper of purified Cu
with Cu
2
Oconcentration of 89.4. During the experimental process it was found that without slag
addition it is very difficult to separate smelt Cu from its container, the corundum crucible, and the
crucible is easy to be broken. To avoid this phenomenon, a part of slag remained together with metal
in the smelting process. The metal obtained is shown in Figure 8. This time it was very easy to
separate the smelted copper from the crucible. The influence of slag remaining rate on silver recovery
is shown in Table 5. It can be seen that higher slag remaining ratio correspond to higher silver
recovery efficiency. When all of the slag remained in the smelting step, the purity of the copper is
higher than 95%.
Experimental Study on Metal Recycling from Waste PCB
160
Table 4. List of Components of Oily Material by GC-MS Analysis on Figure 3
RT Component
Concentr
ation (%)
RT Component
Concentrat
ion (%)
1.38 2-Propenenitrile 0.07 7.63 Quinoline 0.46
1.54 Propenenitrile 0.04 7.72 1,4-Benzenedicarbonitrile 1.30
2.02 Benzene 10.47 7.94 p-Isopropenylphenol 1.30
2.88 Pyridine 0.12 8.04 Naphthalene,2-methyl- 0.56
3.03 Toluene 4.13 8.16 Naphthalene, 2-methyl- 0.86
3.31 Cyclopentanone 0.13 8.61 Biphenyl 2.54
3.73 Pyridine,2-methyl- 0.11 8.66 2-Bromo-p-cymene 0.15
4.08 Ethylbenzene 0.46 9.09 Acenaphtrylene 1.18
4.20 p-Xylene 0.71 9.29 1,1-Biphenyl,3-methyl- 0.27
4.26 Phenylethyne 0.15 9.35 Acenaphthene 0.25
4.42 Styrene 2.46 9.41 Naphthalene 0.17
4.75 Benzene,(1-methylethyl)- 0.1 9.51 2- Naphthalenol 0.19
4.87 Benzene,bromo- 0.1 9.57 Dibenzofuran 0.96
5.31 Phenol 24.71 9.99 Florene 0.73
5.34 -Methylstyrene 0.22 10.28 Dibenzofuran,4-methyl- 0.25
5.45 Benzonitrile 8.07 10.66 p-Hydroxybiphnyl 2.68
5.53 Benzofuran 2.24 11.20 Phenol,2-(phenylmethyl)- 2.97
5.96 Phenol,2-methyl 2.43 11.35 Phenanthrene 0.51
6.14 Phenol,4-melthyl- 1.63 11.50
1H-Indene,1-
(phenylmethylene)-
0.38
6.18 Phenol,2-bromo- 0.35 12.12 2-Phenylnaphthalene 0.68
6.48 Benzonitrile,4-methyl- 1.22 12.63 Fluoranthene 0.61
6.53 Benzofuran,2-methyl- 1.32 12.91 Fluoranthene 0.49
6.77 Phenol,2,4-dinethyl- 0.22 13.32 11H-Benzo()fluorene1 0.23
6.91 Phenoe,4-ethyl- 1.26 14.38 Benz[]anthrcene 0.22
7.07 Hexanedinitrile 0.2 14.80 Triphenylene 0.46
7.21 Naphthalene 11.83 15.88 Benzo[k]fluoranthene 0.23
7.31 Benzofuran,2,3-dihydro- 0.65 16.37 Benzo[k]fluoranthene 0.11
7.38 Phenol,4-(1-methylethyl)- 3.72 16.47 Benzo[k]fluoranthene 0.12
Table 5. Influence of Slag Remaining Ratio on Ag Recovery (%wt)
Slag remaining ratio 0 50.34 69.5 79.1 85.9 100
Ag recovery efficiency 85.4 89.3 94.5 97.7 98.6 99.04

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161

Figure 7 Smelted Cu Without Slag Addition Figure 8 Smelted Cu with Slag Addition
2.2.3 Deoxidization of Cu
2
O
The main purpose in this step is to study the destroy effect of the pollutants in pyrolysis gas. To
realize this purpose the pyrolysis gas was send to the smelting furnace to let it contact with Cu
2
O-
containing slag to oxidizing organics in gas while part of Cu
2
O is reduced to Cu. Simultaneously,
alkali material in the Cu
2
O-containing slag absorbed the acidic gas components in the gas phase.
When originally slag with Cu
2
O content of 30.5% was used and heated from 600 to 1200, the
pyrolysis gas began to contact with slag and the final gas pollutant emission data is shown in Figure 9.
Also the composition of the resulted final slag is shown in Table 6.
From Figure 9. it can be seen that the gas pollutants are only CO and NOx, no Br is detected. And the
emission of CO and NOx decreased as contact time increased (temperature increased too), which
means the high temperature Cu
2
Ocontaining slag is very effective to clean pyrolysis gas.
Table 6 shows that the Cu
2
O in resulted slag decreased. Indeed there was Cu precipitated on the
bottom of the crucible container. Also it can be seen that part if Br can be incepted by alkali slag.
0
100
200
300
400
0 1 2 3 4 5 6 7 8 9 10 11
Contact time (min)
C
o
n
c
e
n
t
r
a
t
i
o
n

(
m
g
/
N
m
3
)
CO
NOx


Figure 9 Gaseous Pollutant Emissions when Pyrolysis Gas Contact with Cu
2
O-Containing Slag
Table 6. Composition of Deoxidized Slag with Pyrolysis Gas (%wt)
Component Na
2
O Al
2
O
3
SiO
2
P
2
O
5
CaO Sn Ti
Content 17.5 1.7 47.4 0.09 0.48 7.71 0.24
Component ZrO
2
SnO
2
Sb
2
O
3
PbO Cl Fe
2
O
3
NiO
Content 0.02 1.4 0.080 0.1 0.03 1.0 0.03
Component Cu
2
O Br
Content 29.0 0.1
Experimental Study on Metal Recycling from Waste PCB
162
3.0 CONCLUSION
Metal recovery from printed circuit boards (PCB) was studied experimentally with a three-step
pyrometallurgy technology: pyrolysis melting followed by smelting process and gas cleaning step.
Experimental results showed that NaOH can be used in the pyrolysis step to help decreasing melting
temperature and separating metal from non-metal slag. Addition of NaOH by 12%wt of PCB resulted
in a copper recovery rate of more than 99% under 1200. The organic substances produced from
pyrlysis process were mainly benzene, 2-butyne and toluene in the gas phase; but 1-Butene, 4-bromo-;
Butane, 1-bromo-; and bromo benzene also appears from 0.02% to 0.06%. In the smelting step order
to purify the recovered Cu and recovery the noble silver, the slag and metal obtained in the pyrolysis
step were smelting together in air flow under 1200; the slag addition helped the separation of metal
from the container and improved the silver recovery efficiency. In gas cleaning step the pyrolysis gas
contacted with the slag from the smelting step under high temperature and the gas pollutants can be
controlled successfully in the smoke; at the same time part of Cu
2
O in the slag was reduced to Cu by
the pyrolysis gas. All the results proved that pyrometallurgy technology to dispose PCB deserves
further investigation.
ACKNOWLEDGEMENTS
This project is supported by Asian regional research program on environmental technology
sustainable solid waste landfill management in Asia funded from Sweden International
Development Agency (Sida).
REFERENCE
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CUI Jirang, Forssberg E. Mechanical recycling of waste electric and electronic equipment: a review,
Journal of Hazardous Materials, B99: pp. 246-251 (2003).
Mecucci, Andrea; Scott, Keith. Leaching and electrochemical recovery of copper, lead and tin from
scrap printed circuit boards. Journal of Chemical Technology and Biotechnology, pp. 449-457
(2002).
ZHAO Yuemin, WEN Xuefeng, SHI Hongxia, JIAO Hongguang, TAO Youjun.Study on Metals
Recovery from -0.074 mm Printed Circuit Boards by Enhanced Gravity Separation. Chinese
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