Proceedings of the International Conference on Sustainable Solid Waste Management, 5 - 7 September 2007, Chennai, India. pp.

155-162

Experimental Study on Metal Recycling from Waste PCB

Gongming Zhou1, Zhihua Luo1 and Xulu Zhai2
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 Cu2O 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 155

Experimental Study on Metal Recycling from Waste PCB

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, electricalconductivity 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 Cu2O 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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Sustainable Solid Waste Management Table 1. Elemental Analysis of PCB in the Experiments (wt %)

Element content Element content Element content

Al 1.59 Pt <0.0027 Au 0.0076

Ca 3.20 As 0.006 Ba 0.16

Fe 0.22 Cr 0.025 Cu 24.69

Mn 0.012 K 0.027 Mg 0.096

Pb 0.63 Na 0.002 Ni 0.11

Sn 2.31 S 0.11 Sb 1.97

Ti 0.09 Sr 0.02 Zn 0.08

Ag 0.0242 Zr 0.016 Pd <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 Cu2O - 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 157

Experimental Study on Metal Recycling from Waste PCB

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 SiO2, Al2O3, 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.
Ratio of NaOH to PCB(%)

20 18 16 14 12 10
1080 1120 1160 1200 M e ltin g te mp e ra tu re ( )

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 158

Sustainable Solid Waste Management

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 content Element content Element content

Al 4.14 Pt <0.004 Au <0.001

Ca 8.30 Pd <0.004 Ba 0.42

Fe 0.18 Ag <0.0006 Cu 0.15

Mn 0.011 K 0.070 Mg 0.25

Pb 0.007 Zr 0.041 Ni 0.002

Sn 0.024 S 0.21 Sb 0.037

Ti 0.24 Sr 0.053 Zn 0.049

Table 3. Composition of Metal Phase (wt%)

Element content Element content Element content

Al 4.14 Pt <0.004 Au <0.024

Ca 0.006 Pd <0.004 Cr 0.083

Fe 0.49 Ag 0.080 Cu 82.247

Mn 0.026 Si 0.006 As 0.02

Pb 2.08 Zn 0.22 Ni 0.35

Sn 7.71 S 0.11 Sb 6.54

Ti 0.24 Na 0.008

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 Cu2O; the Cu2O together with other impurities formed the slag on the upper of purified Cu with Cu2Oconcentration 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%.

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Experimental Study on Metal Recycling from Waste PCB Table 4. List of Components of Oily Material by GC-MS Analysis on Figure 3

RT 1.38 1.54 2.02 2.88 3.03 3.31 3.73 4.08 4.20 4.26 4.42 4.75 4.87 5.31 5.34 5.45 5.53 5.96

Component 2-Propenenitrile Propenenitrile Benzene Pyridine Toluene Cyclopentanone Pyridine,2-methylEthylbenzene p-Xylene Phenylethyne Styrene Benzene,(1-methylethyl)Benzene,bromoPhenol -Methylstyrene Benzonitrile Benzofuran Phenol,2-methyl

Concentr ation (%) 0.07 0.04 10.47 0.12 4.13 0.13 0.11 0.46 0.71 0.15 2.46 0.1 0.1 24.71 0.22 8.07 2.24 2.43 1.63 0.35 1.22 1.32 0.22 1.26 0.2 11.83 0.65 3.72

RT

6.14 Phenol,4-melthyl6.18 6.48 6.53 6.77 6.91 7.07 7.21 7.31 7.38 Phenol,2-bromoBenzonitrile,4-methylBenzofuran,2-methylPhenol,2,4-dinethylPhenoe,4-ethylHexanedinitrile Naphthalene Benzofuran,2,3-dihydroPhenol,4-(1-methylethyl)-

Concentrat ion (%) 7.63 Quinoline 0.46 7.72 1,4-Benzenedicarbonitrile 1.30 7.94 p-Isopropenylphenol 1.30 8.04 Naphthalene,2-methyl0.56 8.16 Naphthalene, 2-methyl0.86 8.61 Biphenyl 2.54 8.66 2-Bromo-p-cymene 0.15 9.09 Acenaphtrylene 1.18 9.29 1,1-Biphenyl,3-methyl0.27 9.35 Acenaphthene 0.25 9.41 Naphthalene 0.17 9.51 2- Naphthalenol 0.19 9.57 Dibenzofuran 0.96 9.99 Florene 0.73 10.28 Dibenzofuran,4-methyl0.25 10.66 p-Hydroxybiphnyl 2.68 11.20 Phenol,2-(phenylmethyl)2.97 11.35 Phenanthrene 0.51 1H-Indene,111.50 0.38 (phenylmethylene)12.12 2-Phenylnaphthalene 0.68 12.63 Fluoranthene 0.61 12.91 Fluoranthene 0.49 13.32 11H-Benzo()fluorene1 0.23 14.38 Benz[]anthrcene 0.22 14.80 Triphenylene 0.46 15.88 Benzo[k]fluoranthene 0.23 16.37 Benzo[k]fluoranthene 0.11 16.47 Benzo[k]fluoranthene 0.12 Component

Table 5. Influence of Slag Remaining Ratio on Ag Recovery (%wt)

Slag remaining ratio Ag recovery efficiency

0 85.4

50.34 89.3

69.5 94.5

79.1 97.7

85.9 98.6

100 99.04

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Figure 7 Smelted Cu Without Slag Addition

Figure 8 Smelted Cu with Slag Addition

2.2.3 Deoxidization of Cu2O 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 Cu2Ocontaining slag to oxidizing organics in gas while part of Cu2O is reduced to Cu. Simultaneously, alkali material in the Cu2O-containing slag absorbed the acidic gas components in the gas phase. When originally slag with Cu2O 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 Cu2Ocontaining slag is very effective to clean pyrolysis gas. Table 6 shows that the Cu2O 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.
Concentration (mg/Nm ) 400 300 200 100 0 0 1 2 3 4 5 6 7 8 9 10 11 Contact time (min)
CO NOx
3

Figure 9 Gaseous Pollutant Emissions when Pyrolysis Gas Contact with Cu2O-Containing Slag Table 6. Composition of Deoxidized Slag with Pyrolysis Gas (%wt)

Component Content Component Content Component Content

Na2O 17.5 ZrO2 0.02 Cu2O 29.0

Al2O3 1.7 SnO2 1.4 Br 0.1

SiO2 47.4 Sb2O3 0.080

P2O5 0.09 PbO 0.1

CaO 0.48 Cl 0.03

Sn 7.71 Fe2O3 1.0

Ti 0.24 NiO 0.03

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Experimental Study on Metal Recycling from Waste PCB

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 Cu2O 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 Bernardes, Andrea; Bohlinger, Isrun; Rodriguez, Diosnel; Milbrandt, Harry; Wuth, Wolfgang. Recycling of printed circuit boards by melting with oxidizing/reducing top blowing process. Extraction and Processing Division (Proceedings of the 1997 TMS Annual Meeting), pp. 363375 (1997). 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 Journal of Process Engineering, pp. 201-204 (2006).

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