Waste Management: Muammer Kaya

Waste Management 57 (2016) 64–90
Contents lists available at ScienceDirect
Waste Management
journal homepage: www.elsevier.com/locate/wasman
Review
Recovery of metals and nonmetals from electronic waste by physical

and chemical recycling processes
Muammer Kaya
Mining Engineering Department, Eskisßehir Osmangazi University, Eskisßehir, Turkey
a r t i c l e i n f o a b s t r a c t
Article history: This paper reviews the existing and state of art knowledge for electronic waste (e-waste) recycling.
Received 2 April 2016 Electrical and/or electronic devices which are unwanted, broken or discarded by their original users
Revised 2 August 2016 are known as e-waste. The main purpose of this article is to provide a comprehensive review of
Accepted 4 August 2016
e-waste problem, strategies of e-waste management and various physical, chemical and metallurgical
Available online 16 August 2016
e-waste recycling processes, their advantages and disadvantages towards achieving a cleaner process
of waste utilization, with special attention towards extraction of both metallic values and nonmetallic
Keywords:
substances. The hazards arise from the presence of heavy metals Hg, Cd, Pb, etc., brominated flame
E-waste
WEEE
retardants (BFRs) and other potentially harmful substances in e-waste. Due to the presence of these
PCB substances, e-waste is generally considered as hazardous waste and, if improperly managed, may
Recycling pose significant human and environmental health risks.
Metal recovery This review describes the potential hazards and economic opportunities of e-waste. Firstly, an overview
Nonmetal recovery of e-waste/printed circuit board (PCB) components is given. Current status and future perspectives of
Hydrometallurgy e-waste/PCB recycling are described. E-waste characterization, dismantling methods, liberation and clas-
Pyrometallurgy sification processes are also covered. Manual selective dismantling after desoldering and metal-nonmetal
Biohydrometallurgy
liberation at 150 lm with two step crushing are seen to be the best techniques. After size reduction,
mainly physical separation processes employing gravity, electrostatic, magnetic separators, froth floata-
tion, etc. have been critically reviewed here for separation of metals and nonmetals, along with useful
utilizations of the nonmetallic materials. The recovery of metals from e-waste material after physical
separation through pyrometallurgical, hydrometallurgical or biohydrometallurgical routes is also
discussed along with purification and refining. Suitable PCB recycling flowsheets for industrial applica-
tions are also given. It seems that hydrometallurgical route will be a key player in the base and precious
metals recoveries from e-waste.
E-waste recycling will be a very important sector in the near future from economic and environmental
perspectives. Recycling technology aims to take today’s waste and turn it into conflict-free, sustainable
polymetallic secondary resources (i.e. Urban Mining) for tomorrow. Recycling technology must ensure
that e-waste is processed in an environmentally friendly manner, with high efficiency and lowered car-
bon footprint, at a fraction of the costs involved with setting multibillion dollar smelting facilities. Taking
into consideration our depleting natural resources, this Urban Mining approach offers quite a few bene-
fits. This results in increased energy efficiency and lowers demand for mining of new raw materials.
Ó 2016 Elsevier Ltd. All rights reserved.
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
2. Printed circuit boards (PCBs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
2.1. Characterization of waste PCBs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
2.2. PCB assembly structure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
2.3. Methods of joining components in PCBs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
3. Physical/mechanical recycling techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
E-mail address: [email protected]
http://dx.doi.org/10.1016/j.wasman.2016.08.004
0956-053X/Ó 2016 Elsevier Ltd. All rights reserved.
M. Kaya / Waste Management 57 (2016) 64–90 65
List of abbreviations
Flame retardants and by-products of e-waste treatment processes LCD liquid crystal display
TV television
BFR brominated flame retardant
PCB printed circuit board
PBDE polybrominated diphenyl ethers
CPU central processing unit
TBBPA tetrabromobisphenol-A
HBCD hexabromocyclododecanes
PBB polybrominated biphenyls Metallurgy
PXDD/Fs mixed halogenated dioxins and furans DSX direct solvent extraction
PBDD polybrominated dioxins SSX synergistic solvent extraction
PCDD polychlorinated dioxins VMS vacuum metallurgy separation
CFC chlorofluorocarbon TBP tribromophenol
Fs furans
PVC polyvinylchloride Characterization equipments
AAS atomic absorption spectrophotometer
E-waste terminology ICP–OES inductively coupled plasma spectrometer
3R reduce, reuse and recycle ICP–MS inductively coupled plasma mass spectrometer
EEE electric and electronic equipment XRD x-ray diffraction
WEEE waste electrical and electronic equipment XRF x-ray fluorescence
EoL end-of-life SEM scanning electron microscope
RoHS restriction of hazardous substances TGA thermo gravimetric analysis
EPR extended producer responsibility
ARF advanced recycling fee General
PGM platinum group metals
Components/parts of electric and electronic equipments IMC inter metallic compound
EC electronic component CCL copper-clad plate
IT information technology SMD surface mounted device
CD compact disc THD through-hole device
DVD digital versatile disc LOI loss of ignition
CRT cathode ray tube TBE tetrabromoethane
3.1. Dismantling (manual, automated and semi automated) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74

3.2. Comminution for liberation of metallic and nonmetallic fractions (shredding/crushing) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
3.3. Sieving for classification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
3.4. Chemical composition determination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
3.5. Gravity separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 77
3.6. Magnetic separation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
3.7. Electrostatic separation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
3.8. Froth flotation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
3.9. Perspectives of physical recycling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
4. Chemical recycling techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
4.1. Perspectives on chemical recycling of the nonmetallic fractions from PCBs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
5. Metallurgical processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
5.1. Pyrometallurgical processes (smelting) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
5.2. Hydrometallurgical processes (leaching) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
5.2.1. Precious and base metal recoveries by acid/alkaline leaching. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
5.2.2. Biohydrometallurgical leaching processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
6. Purification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
7. Alternative uses of nonmetallic fraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
7.1. Perspective of alternative use of nonmetallic fraction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
8. Concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
1. Introduction ments, government office machines (information technology (IT)

and telecom equipments) and private sector offices and industrial
E-waste comprises of waste electric and electronic equipments equipments and machines are main source of e-waste. Consumer
(WEEE/EEE) or goods which are not fit for their originally intended and lighting equipments; electrical and electronic tools; entertain-
use. Such EEEs may be TVs, telephones, radios, computers, printers, ment devices; toys and sports equipments and monitoring and
fax machines, DVDs, CDs, washing machines, refrigerators, dryers, controlling equipments are also important source of e-waste. EEEs
vacuum cleaners, etc. Fig. 1 shows the composition distribution of can become e-waste due to rapid advancement in technology;
e-waste. Half of the e-waste is coming from electrical appliances development in society; change in style, fashion and status; greater
and the rest from electronic goods. Fig. 2 shows the four sources demands on EEE; nearing the end of their useful life and not taking
of e-waste. Small/large home appliances, hospital medical equip- precaution while handling them. The replacement of EEE becomes
66 M. Kaya / Waste Management 57 (2016) 64–90
valuable resources together with plenty of heavy metals and

hazardous materials, which are considered both an attractive
polymetallic secondary source and an environmental contaminant.
E-waste represents a rapidly growing disposal problem worldwide.
Therefore, recycle of valuable metallic and/or nonmetallic materi-
als from them are necessary and compulsory in many developed/
developing countries. With the phenomenal technological
advancement and growth in electronic industries, the number of
consumer and business electronic products per capita has been
raised manifold in the last three decades in tandem with the
downward price of newer products. At the same time, the average
lifetime of electronic products has also been reduced drastically,
resulting in massive generation of End-of-Life (EoL) electronic
goods. The United Nations (UNs) estimate of the global WEEE pro-
duction was 14 million tons in 1992, 24 million tons in 2002,
49 million tons in 2012 and more than 50 million tons today;
and the number is growing at an exponential rate (Fig. 3). The rate
of e-waste generation is increasing by 10% every year (Sakunda,
2013). The USA, China, Japan, Germany and Russia were the biggest
e-waste generating countries in 2012. The USA, Australia and the
UK had the biggest e-waste production per capita in 2012.
Fig. 1. Composition distribution of e-waste. E-waste amount is 5–30 kg per person per year and grows at 3
times faster than the municipal waste (Zhou and Qiu, 2010;
Wang et al., 2015; Kaya, 2016a).
Home Hospitals Government Private Sectors
Table 1 shows the hazardous substance occurrences in WEEE
• PC • PC • PC • PC
• TVs • Monitor • CPU • Boiler and possible adverse affects to the human health. Hg is used in
• Radio • ECG device • Printer • Mixer relays, switches, batteries, liquid crystal displays (LCDs) and gas
• Cell phone • Microscope • Fax • Signal
discharge lamps (i.e. fluorescent tubes in scanners and photo-
• Washing • Incubator • Photocopy conditioner
machine • X ray machine • Incubator etc. copiers). Yearly, about 22% of the Hg produced in the world is used
• Microwave oven machine • Scanner in electronics industry. Rechargeable batteries contain Pb, Cd, Li
• CD player • MR etc. • Fan
and Ni. Old TVs, Personal Computers (PCs) and Cathode Ray Tubes
• Fan • Tube light etc.
• Electric iron etc. (CRTs) contain Pb in cone glass, Ba in electron gun getter and Cd in
phosphors. PCBs have Pb, Sn and Sb in solder; and Cd and Be are
Fig. 2. Four main sources of e-waste. found in switches. Polyvinylchloride (PVC) and BFRs are main com-
ponents of plastics. Cr6+ are found in data types and floppy discs.
Condensers and transformers contain polychlorinated biphenyls
more frequent, which results in large quantities of e-waste need to (PBBs). Chlorofluorocarbon (CFC) can be found in cooling units
be disposed (Zhou and Qiu, 2010). and insulation foams. Americium (Am) can be found in smoke
E-waste is one of the fastest growing waste streams and it has detectors. LCDs include liquid crystals embedded between thin
been estimated that these items already constitute about 8% of layers of glass and electrical control elements. Liquid crystals are
municipal waste (Widmer et al., 2005). E-waste contains lots of mixture of 10–20 substances which belong to the groups of substi-
Fig. 3. Total e-waste generation of some countries in 2012 (https://www.statista.com/chart/2283/electronic-waste/).

Table 1
Hazardous substances in WEEE/EEE (http://slideplayer.com/slide/4776306/).
Substances Occurrence in WEEE Possible adverse effects

Lead (Pb) CRT screens, batteries, PCBs Vomiting, diarrhea, convulsions, coma or even death, appetite loss,
abdominal pain, constipation, fatigue, sleeplessness, irritability and
headache
Mercury (Hg) Fluorescent lambs, some alkaline batteries, switches Brain and liver damage
Chromium VI (Cr6) Data tapes, floppy-discs Irritating to eyes, skin and mucous membranes, DNA
Barium (Ba) Getters in CRT Brain swelling, muscle weakness, damage to the heart, liver and spleen
Cadmium (Cd) NiCd batteries, fluorescent layer (CRT screens), Symptoms of poisoning (weakness, fever, headache, chills, sweating and
printer inks and toners muscle pain), lung cancer and kidney damage
Arsenic (As) Gallium arsenide in light emitting diodes (LED) Skin diseases, decrease nerve conduction velocity, lung cancer
Americium (Am) Smoke detectors Radioactive element
Antimony (Sb) Flame retardants in plastics Carcinogenic potential
Chlorofluoro carbon (CFC) Cooling units, insulation foams Deleterious effect on the ozone layer, increased incidence of skin cancer
and/or genetic damages
Polychlorinated biphenyls (PCB) Condensers, transformers Cancer, effects on the immune systems, reproductive system, nervous
system, endocrine system and other health effects
PBDEs, PBBs Flame retardants in plastics Hormonal effects, under thermal treatment possible formation of dioxins
and furans
recovery option. Open dumping is the most common form of

e-waste disposal in the most developing countries. Burial or land-
fill disposal allows heavy metals to be leached into the ground
water or methane off gassing. Combustion of organic substances
in waste by incineration makes hazardous material airborne,
generates ashes and heat. Leaching of the ashes may cause water
and soil contamination. E-waste constitutes 40% of Pb and 70% of
heavy metals in landfills (Sepülveda et al., 2010; Kaya, 2016b).
BFRs are used in both PVC and in other types of plastics to
reduce the flammability of PCBs, cables and plastic covers of
WEEEs. Incineration has a risk of generating and dispersing con-
taminants and toxic substances. The gases released during the
burning and residue ash is often toxic and requires expensive flue
gas purification systems. Studies have shown that Cu in PCBs and
Fig. 4. Most to least favored options for e-waste management hierarchy (en.
cables acts as catalyst for dioxin formation when BFRs are inciner-
wikipedia.org and www.acceleration.eu). ated. These BFRs when exposed to low temperature (600–800 °C)
uncontrolled burning can lead to the generation of extremely toxic
polybrominated/polychlorinated dioxins (PBDDs/PCDDs and fur-
ans (Fs). PVC which can be found in e-waste in significant amount
tuted phenylcyclohexanes, alkylbenzenes and cyclohexylbenzenes. is highly corrosive when burned and also induces the formation of
These substances contain O, F, H and C and are suspected to be dioxins. Concerns have also been raised about the use of stabilizer
hazardous. Cd metals and phthalate plasticizers in PVC. Phenolic BFRs and
Pb causes damages on human central and peripheral nervous glass fiber are generally used in PCBs (Tsydenova and Bengtsson,
systems, blood systems and kidney. It also affects brain develop- 2011).
ment of children. Cr causes asthmatic bronchitis and damages on Grabda et al. (2009) investigated the bromination of ZnO by
DNA. Cd has a toxic irreversible effects on human health, accumu- thermal decomposition of tetrabromobisphenol (TBBPA). They
lates in kidney and liver. Cd also causes neural damage. Hg causes a found that the bromination of ZnO occurred at 272 °C (DSC) and
chronic damage to the brain and respiratory system. Plastics and above 290 °C (furnace) effectiveness of 41, 64 and 81% dependent
PVC produce dioxins after burning. They cause reproductive and on experimental conditions. Volatilization of the formed ZnBr2
development problems, damage immune system and interfere began at 340 °C and had a yield at 650 °C. Oleeszek et al. (2013)
with regulatory hormones. investigated the distribution of Cu, Ag and Au during thermal
Proper e-waste management for all countries is necessary; treatment with BFRs. They found that 50% of Cu and Ag can evolve
because, e-waste pollutes the ground water, acidifies the soil, gen- from sample residues in the form of volatile CuBr and AgBr above
erates toxic fume and gas after burning, accumulates fastest in 600 and 1000 °C, respectively. Au was resistant to HBr and
municipal disposal areas and releases carcinogenic substances into remained unchanged in the residue. Incineration also leads to the
the air. For a proper e-waste management, the most favored to loss of valuable trace elements which could have been recovered,
least favored option hierarchy pyramid is given in Fig. 4. For a if they had been sorted and processed separately.
proper e-waste management; waste prevention conserves scarce In landfill, e-waste is placed in a hole, compacted and covered
resources; minimization reduces material usage and reuse uses with soil, i.e. buried under soil. It reduces the amount of rats, les-
materials again. They are the most favored options and are on sens the danger of fire and decreases the bad odor. A double liner
top of the e-waste hierarchy pyramid. Burning (i.e. incineration system (i.e. compacted plastic clay and plastic geomembrane liner)
or pyrolysis for energy recovery prior to disposal) and disposal at the bottom prevents liquid waste from seeping into the ground
by landfilling are the least favored options in the e-waste manage- water and collects leachate to seep through the solid waste. Impro-
ment pyramid. Disposal does not conserve any resources. Recycling per treatment of e-waste generates serious soil, air and water
e-waste is an intermediate polymetallic secondary resource pollution problems. Current improper e-waste handling includes:
open burning of circuit boards and cables for metals, hazardous substances (i.e. four heavy metals: Pb, Hg, Cd, Cr6+,
acid/cyanide stripping of valuable metals and and two BFRs: polybrominated biphenyls (PBB), and polybromi-
CRT cracking and dumping. nated diphenyl ethers (PBDE), with some limited exemptions).
The commission decision 2005/618/EC of 18 August 2005 estab-
For a proper e-waste management, EEE producers’ extended lished maximum concentration values of 0.1% by weight in
responsibilities (EPR) include proper labeling the materials to homogenous materials (i.e. plastics, ceramics, glass, metals, alloys,
assist recycling, limit the toxic constituents in the products, use paper, board, resins, coatings) for Pb, Hg, Cr6+, PBB, and PDBE
green/recyclable raw materials in the production, minimize the and 0.01% by weight in homogenous materials for Cd. Manufactur-
waste amount in the product, offer take-back program options, ers are fully accountable for ensuring that their products are in
etc. Responsibilities of governments are implementation of compliance. Failure to comply with the RoHS requirements will
legislations and laws; strict regulations against illegal dumping result in the removal of manufacturers’ products from the market.
of e-waste; heavy fines on industries and encourage non- The purpose of EU directive 2002/96/EC of 27 January 2003 on
governmental organizations (NGOs) for awareness. E-waste WEEE (reuse, recycle, tack-back, recycling cost) is, as a first prior-
includes at least 57 valuable elements found in periodic table ity, the prevention of WEEE, and in addition, the reuse, recycling
(Fig. 5). E-waste contains valuable resources which offer opportu- and other forms of recovery of such wastes so as to reduce the
nities for Urban Mining and job creation. The USA Environmental disposal of waste. It also seeks to improve the environmental
Protection Agency (EPA) and UNs estimate that only 15–20% of performance of all operators involved in the life cycle of EEE, e.g.
e-waste is recycled, the rest of these consumer electronics go producers, distributors and consumers and in particular those
directly to landfills and incineration (United Nations University, who directly involved in the treatment of WEEE. OECD’s Environ-
2009). According to Assocham report in India, only 1.5% of total mentally Sound Management of Waste (Reclaim e-waste) was
e-waste is recycled by formal recycling sector in an environment implemented in 2004. Finally, EUs’ HYDROWEEE (FP7-SME) project
friendly way. The rest is recycled by informal recycling sector in deals with the recovery of base and precious metals from WEEE
the world (http://www.assocham.org/newsdetail.php?id=5725). including lamps and spent batteries by hydrometallurgical
Chronologically serious international programs combating processes. The idea was to develop a mobile plant using hydromet-
e-waste problem are the UNs Development Programme (UNDP)’s allurgical processes to extract metals like Cu, Mn, Zn, In and
Basel Convention (No transboundary movement of hazardous Y in a high purity (>95%) (http://www.4980.timewarp.at/sat/
waste) in 1989. The Swiss Economic Association for the Suppliers hydroWEEE/).
of Information, Communication and Organizational Technology According to the UNs 2014 Global e-Waste Surveillance Report,
(SWICO) was proposed e-waste project with an Advance Recycling 503,000 tons of e-wastes were produced in Turkey (http://unu.
Fee (ARF). The Swico recycling system has been developed to edu/news/news/ewaste-2014-unu-report.html). E-waste amount
ensure that WEEE could be taken back free of charge in Switzerland was 6.5 kg/person in 2014. Turkey is the 17th biggest e-waste pro-
since 1994. Japan’s Home Appliances Recycling Law (i.e. take-back, ducer in the world. Between 2006 and 2012, about 30,500 tons of
recycle end products) was implemented in 2001. WEEEs were collected and separated in Turkey by 30 licensed recy-
Restriction of the use of certain Hazardous Substances in elec- clers. Waste PCBs with electronic parts are exported to Belgium,
trical and electronic equipment (RoHS) directive (2002/95/EC) Germany and France for further recycling from Turkey. In the EU,
brings restriction for complement of EEE that are shipped to the 9.3 million tons of e-waste was collected and only 35% of them
European market after the 1st July 2006 and limits the use of six are recycled in 2012. 50–80% e-waste collected in the USA and
Fig. 5. Valuable elements found in e-waste (http://slideplayer.com/slide/4776306/).

Fig. 6. Export of e-waste in the world.
other developed countries exported to third world countries. 2015). According to 2014 UNs’ e-waste report, yearly about
E-waste export map is shown in Fig. 6 (http://ewasteguide.info/ 300 tons of Au were recovered and the e-waste market size was
europe-breaking). 52 billion dollars. It has been proved that it is worthwhile to recy-
PCBs represent the most economically attractive portion of cle electronic scrap in spite of the fact that the content of precious
WEEE and account for the weight for about 3–5% (Jiang et al., metals (Au, Ag and Pd) steadily decreases (http://unu.edu/news/
2012; Kaya, 2016b). Waste PCBs constitute a heterogeneous mix- news/ewaste-2014-unu-report.html).
ture of metals, nonmetals and some toxic substances. By contain- E-waste, in particular waste PCBs, represents a rapidly growing
ing many electronic components (ECs), such as resistors, relays, disposal problem worldwide. Considering that the lifetime of a
capacitors, and integrated circuits (ICs), waste PCBs have a metal mobile phone is approximately 1 year and of a computer 2–5 years,
content of nearly 30% Cu;10–20%, solder Pb; 1–5%, Ni; 1–3%, Fe; it is estimated that about 100 million mobile phones and
1–3%, Ag; 0.05%, Au 0.03%; and Pd 0.01%, especially the purity of 17 million of computers are discarded annually in the world due
precious metals in PCBs is more than 10 times that of rich minerals to malfunctioning equipment or because technologies become
(Zhou and Qiu, 2010). It can be seen clearly that except the obsolete. There are several factors to consider in developing a
hazardous substances, a lot of valuable materials contained in PCBs new recycling technology for waste PCBs driven by innovations,
make them worth being recycled. Therefore, developing a social and environmental impact, an integrated waste management
non-polluting, efficient and low cost processing technology for policy and economy of the process. Some of the key factors are:
recycling of PCBs can not only avoid environmental pollution, but
also help to recycle valuable resources, which have a great The waste PCBs are diverse and complex in terms of type, size,
significance for continuous improvement of the human living shape, components and composition. With time, the composi-
environment, standards and resources recycling. tion of PCBs is continuously changing, making it more difficult
In the USA, e-waste recycling ratio for computers in 2010 was to obtain a stable material composition.
40% (423,000 t), monitors 33% (595,000 t), mobile phones 11% The presence of plastics, ceramics and metals in PCBs in a
(19,500 t), keyboards and mice 10% (67,800 t) and TVs 17% complex manner leads to great difficulty in liberation and
(1,045,000 t). In the USA, about 40,000 mobile phones discarded separation of each fraction.
every day (www.powershow.com). A personal computer material Presence of numerous metallic elements leads to a very
composition includes about 26% silica/glass, 23% plastics, 20% fer- complex recovery process. The recovery process becomes more
rous metal, 14% Al and 17% other metals (such as Pb, Cu, Zn, Hg, complicated when the elements are available in ppm
and Cd). A CRT panel contains 0–2% Pb, frit 65–75% Pb, funnel glass concentration.
22–25% Pb and neck 28–30% Pb. A 43 cm CRT monitor contains The driving force for recycling is the recovery of metal values,
about 950 gr Pb. Manufacturing of a computer and monitor which is nearly 30% of the total weight of waste PCBs. The non-
requires 240 kg fossil fuels, 2.2 kg chemicals, 1.5 tons of water. metallic materials (70%) have rather less economic values (i.e.
Recycling 1 million laptops saves the energy equivalent to the elec- filler material).
tricity used by 3657 homes a year. 41 smart phones contain about The objective of most recycling processes is to recover maxi-
1 gr of Au. Every year 1 million smart phones recycled and 16 tons mum metallic values from waste PCBs but sometimes these
Cu, 350 kg Ag, 34 kg Au and 1.5 kg Pd can be recovered. processes are not very environment-friendly.
Besides all the hazards originating from e-waste, manufacturing
mobile phones and PCs consumes considerable fractions of the Au, 2. Printed circuit boards (PCBs)
Ag and Pd mined annually worldwide. 43% of total production of
gold in the world is used in electronics. A large fraction of the PCBs, the base of electronics, are essential part of almost all of
WEEE precious metals is found on the PCBs. Since PCBs as the electronic products. PCBs are used to mechanically support
becoming more complex and smaller, the amount of materials is and electrically connect electronic components using conductive
constantly changing. 1 tons of circuit boards can contain between pathways, tracks or signal traces etched from Cu sheets laminated
80 and 1500 g of Au and between 160 and 210 kg of Cu. These onto a non-conductive substrate. PCBs are integral part in majority
concentrations are 40–800 times the amount of gold in Au ore, of electronic systems and are commonly found in consumer elec-
and 30–40 times the concentration of copper in Cu ore mined in tronics. PCBs constitute at least 3% of the total electronic scraps
the USA. Globally, 267.3 tons of Au and 7275 tons of Ag are by weight. Most recycling approaches practiced can only recover
consumed annually by electronic industry (Vats and Singh, metal contents of PCB scraps to an extent 30% of the total weight.
More than 70% of PCB scraps cannot be efficiently recycled and are used because of their conductive properties. There are two
recovered and have to be incinerated or land filled (Li et al., 2004). types of PCBs (FR-4 and FR-2) normally used in PCs and mobile
PCB assemblies contain a green/yellow board and ECs (i.e. resis- phones. The FR-4 type is composed of a multilayer of epoxy resin,
tors, relays, capacitors and integrated circuits (chips)) attached to fiberglass coated with a Cu layer. The FR-2 type is a single layer of
it. PCBs are a mixture of phenolic/cellulose paper (yellow and fiberglass or cellulose paper and phenolic coated with the Cu layer
low grade) or epoxy (green and high grade) resins, woven glass (William and Williams, 2007; Murugan et al., 2008). Both resins
fiber and multiple kinds of metals (Cu, Sn, Pb, etc.). The basic are thermosetting (i.e. cannot be remelted and reformed). The
structure of the PCBs is the Cu-clad laminate consisting of fiber FR-4 type is used in small devices such as mobile phones and
glass-reinforced epoxy resin and a number of metallic materials FR-2 type is used in televisions and household appliances such as
including precious metals. The concentration of precious metals PCs (Ladou, 2006). The FR-4 epoxy resins are green in color and
especially Au, Ag, Pd and Pt is much higher than their respective have high value while the FR-2 phenolic resins are yellow/brown
primary resources, making waste PCBs an economically attractive in color and have low value.
Urban Mining source for recycling. Additionally, PCBs also contain Table 2 shows the content of PCBs with ECs. PCBs without ECs
different hazardous elements including heavy metals (Cr, Hg, Cd, contain about 30% metals and 70% nonmetals. The nonmetallic
etc.), rare earth elements (Ta, Ga, etc.) and flame-retardants (Br fractions consist of cured thermosetting resins, glass fiber, ceram-
and Cl) that pose grave danger to the eco-system during conven- ics, BFRs, residual metals (Cu and solder) and other additives.
tional waste treatment of landfilling and incineration (Li et al., Nonmetallic fractions composition contains 65% glass fiber, 32%
2004). epoxy resin and impurities (Cu: <3%, solder <0.1%) by weight
Many research works have revealed that the composition of (Yokoyama and Iji, 1997). Resins are organic plastic polymers, high
metals, ceramic and plastics in PCBs with ECs could reach 40%, cost and low quality products. If resins are land filled or incinerated
30% and 30%, respectively (Sum, 1991; Tenorio et al., 1997; like in the past, they create potential environmental problems.
Ghosh et al., 2015; Kaya, 2016a). Meanwhile, the concentrations Glass fibers, which are about 50–70% of PCBs, are reinforcing
of precious metals such as Au and Pd in waste PCBs are richer than material in PCBs.
in natural ores, which makes their recycling important from both Material content of the nonmetallic recycled from waste PCBs
economic and environmental perspectives. Waste PCBs have been by air classification showed that residual Cu and glass fiber were
paid much more attention from researchers and enterprises, not in fine-size class and resins were in coarse-size class (Koyanaka
only due to their rich resource content, but also due to their et al., 1999; Vidyadhar and Das, 2012; Zhou and Qiu, 2010;
potential risk for environment and human health with informal Yamane et al., 2011; Sum, 1991). The thermal stability of non-
recycling. Therefore, factors affecting the extraction of metals are metallic fraction is very important both for physical and chemical
economic feasibility, recovery efficiency and environmental recycling methods, but the demands for the thermal stability in
impact. PCB recycling process with the aim of highest recovery of two methods are just the opposite. In physical recycling, the non-
metallic fraction usually includes three stages: metallic fractions have to be thermal stable in the injection or com-
pression molding. For chemical recycling, the energy cost will be
pretreatment (i.e. composition analysis and manual/automatic/ economical if the degradation temperature of the cured thermoset-
semiautomatic selective disassembly of the reusable and toxic ting resins in the nonmetallic fraction is too high (Guo et al., 2009).
electronic parts by thermal/chemical desoldering) (Jianzhi Nonmetallic fractions thermo gravimetric analysis (TGA) studies
et al., 2004), showed that, degradation was greatest at 343 °C and the onset
size reduction and separation including comminution and sep- temperature was 323 °C. At 471 °C about 60% and at 800 °C about
aration of materials using mechanical/physical processing (such 33% residual weight remained and most of resins were decom-
as shredding, crushing, pulverizing (100–300 lm), screening, posed. Because the upper temperature in most molding process
and upgrading) (Cui and Forssberg, 2003; Veit et al., 2005; Cui is below 323 °C, the thermal stability of the nonmetallic fraction
and Zhang, 2008; Tilmatine et al., 2009; Guo et al., 2011; Tan is good enough for physical recycling methods for the nonmetallic
et al., 2011; Kasper et al., 2011; Tuncuk et al., 2012) and fractions. As for chemical recycling methods, the degradation
metallurgical/chemical (pyro/hydro/electro/biohydro metallur- temperature below 471 °C is reasonable (Guo et al., 2009).
gical processes) refining/purification (Dorella and Mansur, 2007;
Pranolo et al., 2010; Provazi et al., 2011; Lister et al., 2014). 2.2. PCB assembly structure
2.1. Characterization of waste PCBs All PCBs essentially consist of three basic parts:
Due to the diverse and complex nature of waste PCBs, charac- a non-conducting substrate or laminate,
terization in terms of types, structure, components and composi- conducting Cu substrate printed on or inside the laminate and
tion is important to establish the route and process for recycling. the components attached to the substrate (chips (Ga, In, Ti, Si,
Thin films of Sn or Ag are used in the PCBs to protect against Ge, As, Sb, Se and Te), connectors (Au, Ag), capacitors (Ta, Al),
oxidation (Veit et al., 2005). The base metals mainly found in PCBs etc.).
Table 2
PCB types, contents and properties.
Board/substrate Single sided Double sided Multiple layered

Resın Type Color Value
FR-2 (reinforcement) Phenolic cellulose paper Yellow/brown Low value EEE (TV, home electronics)
FR-4 (reinforcement) Epoxy glass fiber Green High value EEE (PC, phones)
Glass fiber/cellulose FR-4 FR-4 FR-4
FR-2 FR-2 FR-2
Cu substrate
Solder Sn, Pb
Electronic components (IC) Chips, ICs, relays Connectors, capacitors Resistors, switches
Table 3 approximately one-fourth organic resin materials containing

PCB material composition. elements such as C and H, and approximately one-third glass-
Metals (%) Ceramics (%) Plastics (%) materials used as resin reinforcing fibers. In terms of metal compo-
about 40% about 30% about 30% sition, the highest content was Cu, which is used in the circuitry,
Cu 6–27 SiO2 15–30 PE 10–16 followed by Sn, Fe and Pb, which is used in the soldering and lead
Fe 1.2–8.0 Al2O3 6.0–9.4 PP 4.8 frames. Interms of the precious metal composition, Au, Ag and Pd
Al 2.0–7.2 Alkali-earthoxides 6.0 PS 4.8 are found in ICs as contact materials or as plating layers due to
Sn 1.0–5.6 Titanates-micas 3.0 Epoxy 4.8
Pb 1.0–4.2 PVC 2.4
their high conductivity and chemical stability (Jung and Bartel,
Ni 0.3–5.4 PTPE 2.4 1999; Takanori et al., 2009). Table 3 shows representative material
Zn 0.2–2.2 Nylon 0.9 compositions of PCBs by percent of weight used in 11 previous
Sb 0.1–0.4 studies (Duan et al., 2011). The material present in PCBs can be cat-
Au (ppm) 250–2050
egorized in three groups: organic materials, metals and ceramics.
Ag (ppm) 110–4500
Pd (ppm) 50–4000 Table 4 shows materials and their properties in PCBs from EoL
Pt (ppm) 5–30 e-waste. Organic materials in PCB are mainly composed of plastics
Co (ppm) 1–4000 with contents of flame-retardants, resins and paper. The type of
plastics is predominantly C-H-O and halogenated polymers. Metals
in PCBs consist of a large amount of base metals; such as Cu, Fe, Al
Depending on the structure and alignment, PCBs can be classi- and Sn; rare metals like Ta, Ga and other rare platinum groups
fied as single-sided, double-sided or multilayered. Single and metals (PGMs); noble metals such as Au, Ag, and Pd. Hazardous
double-sided PCBs have the conducting layer on one or both sides metals such as Cr, Pb, Be, Hg, Cd, Zn, Ni are also present. Ceramics
of the laminates and with or without plated through-holes to inter- present in the PCB are primarily silica and alumina. Other ceramic
connect the sides. PCB board thicknesses can change from 0.2 to materials include alkaline earth oxides, mica and barium titanate.
7.0 mm. Cu thickness on the PCBs are between 17.5 and 175 lm. WEEE plastics contain BFRs, including PBB and PBDEs, and the
Minimum drill hole diameter is 0.2 mm. Solder types are water combustion of these produces the formation of highly toxic gases.
soluble solder paste, leaded and lead free. Surface finishing is gen- Thermoset resins cannot be reformed or reshaped because of their
erally HALS, HALS lead free, chemical Sn, chemical Au, ENIG, net structure; thus, they are regarded as nonrecyclable. PC scrap
immersion Au/Ag or Au plating type. primarily contains ABS, PS and PVC plastics with the density range
PCB assembly weights of some consumer electronics are: CRT of +1.0 to 1.5 g/cm3, whereas PCB scrap mainly contains glass fiber
TVs 7%, computers (PC) 18.8%, mobile phones 21.3% and LCD reinforced epoxy resins plastics with the density range of +1.5 to
screens 11.9% (Duan et al., 2011). Waste PCBs contain 33% semi 2.0 g/cm3 (Zhang and Forssberg, 1997).
conductors, 24% capacitors, 23% unpopulated circuit boards, 12%
resistances and 8% switches and other materials by weight 2.3. Methods of joining components in PCBs
(Tohka and Lehto, 2005). Many components are still functional
and valuable. According to Takanori et al. (2009), the PCBs Electronic components are mounted on PCB assemblies using
contain about one-third metallic materials such as Cu and Fe, various types of connections. These connections are typical of
Table 4
Materials and their properties in PCB assemblies from EoL e-waste.
Materials in PCBs from End-of-Life (EoL) Electronics Scrap
(Heterogen, complex & easy to liberate due to weak interfacial bonds; respected as a poly-metallic secondary source)
Organic Material Ceramic Non-organic Material
Non-metallic Metallic
Non spherical in shapes aer grinding Spherical in shapes aer grinding

Brile fracture (report fines (-1.2 mm)) Malleable/ducle (don't shaer into fines (1.2-5 mm))
Best sizes: (-0.6 and 0.6-1.2 mm) (Al, Ni, Fe → +5.0 mm) but, (Cu, Sn, Pb → 0.6-5.0 mm) (Cu → 1.2 mm)
Density: 1.0-1.8 gr/cm 3 Density: 2.6-19.3 gr/cm3
Polymers (Plascs) Flame Retardants Glass-Fiber Ferrous Metals Nonferrous Metals

(Naturally hydrophobic) (Toxic) (Abrasive) (Non-conducve) (Elemental metals and alloys)
Mass Fracon 30% 30% 40%
(PE, PP, PVC (F, Cl, Br) (Fibers, Silica, alumina (Fe, Ni)* (Cu, Al, Pb, Sn**, Zn, Cr, Hg, Cd etc)
PTFE, nylon, (BFR, PBB, PBDE) epoxy resins, mica, barium tanate,
PPE, Epoxy) TBBPA) alkaline earth oxides
Hazardous Precious Rear Earth Elements

(recyclable) Termoset Metals Metals
(Non-recyclable) (Cr, Hg, Cd, Be, Ni, Zn, Pb) (Au, Ag, Pt, Pa) (Ta, Ga, PGMs)
Analysis: Loss on Ignion (VOC) (800oC)/Argon Difference Aqua regia leaching
* Ferro magnec ** Dia/Paramagnec

Table 5 higher than soldering Sn. However, IMCs are often brittle. Thus,
Solder alloys using in PCB packaging. both the assistance of gravity force (or artificial action) and shear
Element Melting point Eutectic Melting point of stress caused by temperature change are necessary to remove
(°C) composition eutectic solder (°C) soldering Sn (Duan et al., 2011).
Cd 320.8 67Sn33Cd 176 Legislation promotes new Pb-free welding technologies to
Pb 327.5 63Sn37Pb 183 reduce the damage to both humans and the environment. The
Zn 419.4 91Sn9Zn 199 eventual elimination of Pb-based solder has major implications
Ag 960.8 96.5Sn3.5Ag 221
Cu 1083.1 99.3Sn0.7Cu 227
for the processing, assembly, reliability, and electronic packaging
Al 660.1 99.5Sn0.5Al 228 cost aspects due to the solder melting temperature, processing
Mg 651.0 98Sn2Mg 200 temperature, wettability, mechanical and thermo-mechanical fati-
gue, and so on (Guo, 2007). Special liquor, methylphenyl silicon oil,
kerosene, molten salts (LiCl-KCl) or solder can be used as the med-
following type: socket pedestal (press-fit), through-hole device ium to transmit heat to melt solder from the PCB assemblies in
(THD) (wave type solder), surface mounted device (SMD) (solder desoldering pretreatment process (Huang et al., 2009; Flandinet
by reflux), screw joint, and rivet. There are several methods by et al., 2012; Riedewald and Gallagher, 2015).
which these connections can be broken. For example, components
with socket pedestal connection can be disassembled directly by
nondestructive force, but the method used to disassemble compo-
nents with SMD or THD connections are always destructive, 3. Physical/mechanical recycling techniques
involving removal of solder or pins (Ghosh et al., 2015).
Welding is a process through which chemically and mechani- Physical processes are usually employed during the upgrading
cally two metals are joined at a low melting point. Welding occurs stage when various metals and nonmetals contained in e-waste
at a temperature of 40 °C above the melting point of the solder are liberated and separated by some kinds of shredding and crush-
alloy, and is valid for any type of solder, including electronic welding processes. The drive to recover the valuable metals in particular
ing. It has a relatively low melting point (183 °C), good wettability, Au, Ag, Pd and Cu has received tremendous attention in recent
good mechanical and electrical properties and low cost (Marques years using extraction processes such as physical, chemical and
et al., 2013). The oldest and most common Pb-based solders are hydro/pyrometallurgical leaching separation techniques. Method-
63Sn-37Pb. Table 5 shows solder alloys using in PCB packaging. ology generally includes PCB assembly desoldering pretreatment
Melting points of solder alloys (desoldering) change between 176 for ECs removal, size reduction for liberation and a combined route
and 228 °C. of physical and metallurgical processing. Physical recycling
The Sn-Pb alloy, particularly those near to the eutectic compo- techniques include crusher, pulverizer, classifier and separator.
sition, are used as solders while the main substrate or leads are The outcome of a recycling process can be evaluated from two
made of Cu. Sn in the solder readily reacts with Cu to form inter- aspects: the material (i.e. metal and nonmetal) recovering effi-
metallic compounds (IMC) as film at the interface during the solder ciency and the environmental impact of the processing. Physical
reflow process. The cross-section of the samples in the soldered separation processes benefit from low capital and operating costs
conditions showed only a single layer of g phase (Cu6Sn5) at the and suffer from a high valuable metal loss (10–35%) due to insuffi-
interface, and the values are in a range of 1.6–2.3 lm (Tu and cient metal liberation.
Zeng, 2001). Cu6Sn5 starts to melt at 415 °C whereas Cu3Sn starts Physical processes include dry crushing and pulverizing and
to melt at 676 °C (Fields et al., 1991). Fig. 7 shows micrographs then high voltage electrostatic separation to obtain a mixture of
of cross section of the joint. The morphology of the phase layer metal powder (Cu, Pb, Zn, Al, Sn, Au, Ag, etc.) which is conductor
depends on the Pb content of the solder (Prakash and Sritharan, and nonmetallic resin powder material which is not conductor.
2004). Formation of IMC film is imperative for good wetting and To avoid dust pollution three-stage dust removal equipments (i.e.
bonding, but an excessively thick film is harmful because of its cyclone, bag and air cleaner) are used. The separation efficiency
brittleness, which makes it prone to mechanical failure under of this type of physical PCB recycling systems is up to 99% (http://
low loads. The mechanical properties for solder joints are sensitive wqjx.en.alibaba.com). A physical dry PCB recycling production line
to temperature and strain rate. Melting point of IMC is much layout is given in Fig. 8 (http://www.alibaba.com/product-detail/
1000-kgs-hr-high-capacity-low_60315058657.html?spm=a2700.
7724857.29.91.vnNofk). This physical separation plant separates
mixed metal powders from plastic resins using a shredder, pulver-
izer, cyclone classifier, air cleaning equipments, vibrating screens
and electrostatic separator. This type of dry separation plants must
be dust and noise free and can process waste PCBs with or without
ECs, Cu-clad plate – (CCL) and scrap circuit boards.
There are many dry and wet Chinese PCB recycling machine
manufacturers and turn-key project producers from a capacity
between 1–10 t/d and 1500–10,000 t/y. Fig. 9 shows a small
500 kg/h e-waste recycling plant picture. This type of PCB recycling
plants has no waste water and no smoke; requires only one or two
workers to operate and is highly automated. This plant also
requires small space. Cable wire recycling can be achieved by dry
shredding and air classification to separate Cu from plastic
material. 80–800 kg/h capacity machines are available with 99%
separation efficiency (Fig. 10). These type of machines accept
cables with a diameter between 0.5 and 25 mm. Cables contain
Fig. 7. Cross-sectional SEM images of eutectic Sn-Pb solder cap on a Cu foil (Prakash about 40% Cu and 60% PVC plastic. Cu and PVC powders are
and Sritharan, 2004). obtained from these machines separately.
Fig. 8. Waste PCB recycling production line layout (with the permission of Henan Machinery & Equipment Com. Ltd.).
Fig. 9. 500 t/h capacity PCB recycling plant view.
Fig. 10. Dry cable wire recycling machine set and products obtained after separation.
Wet PCB recycling plants have wet gravity separators (i.e. shak- Actually, this informal dismantling technology is still employed
ing tables) to separate high density and coarse mixed metals from with simple improvements by using electric heating plate, with
low density and fine plastics/resins. Cables, wires and waste PCB exhausted gases collected (Duan et al., 2011). Disadvantages of this
can be processed in this system. process are bad smell, black fumes and being a banned process.
On the basis of assembly of PCBs, two methods can be used for
3.1. Dismantling (manual, automated and semi automated) automatic disassembly: selective disassembly and simultaneous
disassembly:
Disassembly/dismantling is the systematic removal of compo-
nents, parts and/or a group of parts from e-waste. Attachment In selective disassembly, some specific components are located
regimes of materials encountered in electronic scrap are fastening, and removed. The connection type and coordinates of connec-
inserting, welding, binding, wrapping, coating and plating. tion are determined and components are disassembled
Basically, it is not energy intensive to unlock the associated mate- individually. This principle is called ‘‘look and pick”.
rials such as ceramics, glasses and metals with different mechani- Under simultaneous disassembly, the whole flat board is heated
cal properties, depending on the locking regimes of materials in a tin furnace to desolder components from the board and all
involved. In general, materials locked through fastening by screws, components are ‘‘wiped off” simultaneously. These components
clinks and rivets, etc., inserting, wrapping and packaging can read- are then identified and sorted by geometrical and physical
ily be detached. Materials locked by means of coating, binding, criterions. This principle is also called ‘‘evacuate and sort”.
welding and encapsulating are relatively difficult to be unlocked Simultaneous disassembly method has high efficiency, but also
and materials locked by alloying and filling cannot be liberated a higher risk of damaging the components. This method also
by mechanical means (Zhang and Forssberg, 1997). Fig. 11 shows requires an additional sorting process that increases the
the hazardous and non-hazardous components in e-waste materi- processing time and cost. In the ‘‘evacuate and sort” system,
als. Hazardous material (CRTs, batteries, some circuit components the components are identified and sorted on the basis of geom-
and Hg containing lamps and switches) should be removed from etry, density, or using magnetic effect. This recognition process
e-waste before metal recycling. is different from the one in selective disassembly.
There are two forms of dismantling: selective and simultaneous
disassembly. Selective dismantling can also be performed manu- The components reuse-oriented selective disassembly is an
ally or mechanically. Currently, manual informal dismantling is indispensable process, since the reuse of valuable components
common in developing countries and mechanical dismantling is has first priority, dismantling the hazardous components is essen-
common in developed countries (Chi et al., 2011). Mechanical tial, and it is also common to dismantle highly valuable compo-
dismantling can be done by either semi-automatic or automatic nents and highly graded materials such as battery in order to
way. Informal manual dismantling aims to heat the solder above simplify the subsequent recovery of materials.
melting point (i.e. desoldering) and resell the reusable ECs. Infor- Mechanical dismantling can be performed by semi automatic
mal manual dismantling uses chisels, hammers and cutting torches approach or intelligent and automatic approach. In semi automatic
to open solder connections and separate various types of metals dismantling, the ECs on the PCBs are removed by a combination of
and ECs. PCBs are cooked over a coal-heated plate in order to melt heating them above melting point of solder and applying external
and resell the chips and other recovered components to acid strip- forces such as impact, shearing, and vibration in part removal unit.
pers for further processing (Huang et al., 2009). The components Infrared heaters at 240–250 °C are required. These types of
are heated using electric blower and then separated by dint of pli- machines include exhausted gas controlling unit, solder removal
ers. Different types of components are put into corresponding bins. unit and bare board collection units. Park et al. (2015) developed
Fig. 11. Hazardous and non-hazardous materials in e-waste (http://www.liquidtechnology.net/computer-e-waste-recycling-disposal/).

an apparatus for ECs disassembly from PCB assembly in e-waste. 2004; Schubert and Bernotat, 2004). Schubert and Bernotat
94% maximum disassembly ratio was obtained at a feeding speed (2004) gave a good review of the different modifications of the
of 0.33 cm/s and a heating temperature of 250 °C by them. swing hammer mills; the comminution mechanism is essentially
Daily 800 kg capacity machines are available today (Duan et al., the same. It breaks mostly by impact, with shear, compression
2011). Solder baths and liquids as a heating medium at 215–230 °C and abrasion; a combination of stress modes appropriate for the
for desoldering pretreatment and mechanical vibration can be diverse material types, from brittle to ductile, present on PCBs.
used. 500 kg per day capacity equipments are available today. The product discharges through a screen – basically, a closed
The use of liquids has two disadvantages: disposing the used fluid circuit grinding. Discharge size below 500 lm is necessary for
and cleaning the bare boards and components for further process- liberation. If we use froth flotation for separation, then 74 lm
ing (Duan et al., 2011). Harruta et al. (1991) reported on using two is enough for total liberation (Ogunniyi et al., 2009).
(mild and strong) oxidation capability reagents in two steps to The PCBs were first cut with a bench guillotine into roughly
remove a layer of Sn and Sn-Pb alloy from PCBs for desoldering. 4–6 cm fragments appropriate for the choke of the swing hammer
In modular semi-automatic systems; disassembly cells consist mill (Eriez magnetics MACSA Pedestal Type Model 300) used for
of a transportation system, a vision system and heating- the fine crushing and grinding. 75 + 38 lm is enough for libera-
desoldering stations. In this mechanical approach, PCBs are fixed tion. Very few composite particles remain. Pb would be inseparable
on frames and fed into the dismantling cell. Vision system identi- from neither Zn nor Sn in a solder particle. A realistic pursuit will
fies reusable parts and toxic components by image processing. be to recover as much as possible of the metallic values in bulk into
Using 3D pictures, applying hot air type of heaters and vacuum a product fraction (Ogunniyi et al., 2009). Beneficiation operation
grippers, reusable and toxic parts are removed. SMD/THD compo- therefore cannot attempt to separate such alloy particles into con-
nents are removed by hot liquid and parallel jaw grippers stituent elements; realistic schemes can aim only at achieving
(Kopacek, 2005; Duan et al., 2011; Kopacek and Kopacek, 2015). some bulk collection of metallic values into a concentrate.
Japanese NEC corporation system comprises two infrared heating Cu is found between layers of resin. Ferromagnetics and Cu
units and two removal units. The first removal unit is equipped liberate at 2 mm and Al at +7 mm (Zhang and Forssberg, 1997).
with impacting brush and the second shearing propellers. The PCB scraps having small size particles can be separated by var-
Automatic disassemblers are expensive and ideally suited for ious separation methods like: size, density, magnetic, electrostatic,
high-metal content waste (Duan et al., 2011; Park et al., 2015). Eddy current and gravity separation. Zhang and Forssberg (1997)
studied the liberation characteristics of PCBs and the effect of
3.2. Comminution for liberation of metallic and nonmetallic fractions shape and size on liberation. It was concluded that below 6 mm
(shredding/crushing) size, ferromagnetic and Cu are completely liberated and at the
same time, Al is found to be liberated in much coarser fraction.
An effective liberation of various materials like metals and plas- Koyanaka et al. (1999) reported that glass fiber-reinforced epoxy
tics is a crucial step towards mechanical separation. In addition, resin undergoes brittle fracturing more readily than metallic mate-
classification of electronic scrap is also important to be able to rials and concentrates in the finer fraction during impact milling of
provide an appropriate feed material for the subsequent physical/ PCB scraps. Yoo et al. (2009) demonstrated the use of stamp mill
metallurgical separation process (Zhang and Forssberg, 1997). for the liberation of various metallic components. Vidyadhar and
The purpose of shredding/crushing is to strip metals from PCBs. Das (2012) also reported that after milling to below 150 lm size,
Crushing technology is intimately related to not only energy con- no interlocking of metallic and nonmetallic particles is observed.
sumption, but also further selective efficiency. Waste PCBs are Wang et al. (2015) investigated the dust as the byproduct originat-
comprised of reinforced resin and metal parts such as wires and ing from mechanical recycling process of waste PCBs from the
joints. Comminution of waste PCBs and high effective liberation viewpoints of resource reuse and environmental protection. Their
of the metal composition from nonmetals is the prerequisite of mineralogical analysis on the dust collected from a typical crushing
the following sequence separation for better recovery of waste and separating recycling line demonstrated 73.1% organic matters,
PCBs. Jiang et al. (2012) claims that shredding or grinding may lead 4.65% Al, 4.55% Fe, 2.67% Cu and 1.06% Pb. Most of the metals lib-
to 40% loss of precious metal and/or to the formation of dangerous erated at 0.75 mm size fraction and as the particle size decreases,
metal fines, dust containing BFRs and dioxins. the content of liberated elemental metals and magnetic materials
A potential process flowsheet for metals recovery from e-waste increase.
with two step crushing, gravity, magnetic, electrostatic physical Shredder is used to reduce the dimension of the material
separations and metallurgical separations is given in Fig. 12 by through cutting, tearing and extruding. It provides a good quality
the author of this review. Much dust and harmful gas can be gen- and reliable equipment for early broken of the e-waste recycling
erated during the crushing process because of the strength and and volume reduction treatment. Double shaft shredder is widely
tenacity of the PCBs. Therefore, a very good dust collection system used in waste plastic, waste rubber, wood and e-waste recycling.
must be used. Fig. 13 shows the PCBs before and after shredding. Diameter of
After removal of the hazardous components (i.e. capacitors, shredder blades changes between 200 and 400 mm, capacity
CRTs, LCD and batteries), different mineral processing unit between 200 and 2500 kg/h, quantity of blade between 16 and
operations such as shredding, crushing and grinding can be used 42 and feed inlet size between 700–760 and 1880–1090 mm.
to liberate metals from cladding materials such as resin, fiberglass Fig. 14 shows the layout of 1000–1200 kg/h PCB dismantling
and plastics. Various types of hammer crushers, rotary crushers, machine, double shaft shredder, hammer mill, air separator, dust
disc crushers, shredders, cutters equipped with a bottom sieve, collector, magnetic and electrostatic separators and cycloning units.
are used for liberation. Ball milling and disc milling are also
reported for pulverizing the PCBs after cutting into small sizes 3.3. Sieving for classification
(Ghosh et al., 2015). Low speed high torque shear shredders
(10 mm) are basically ideal for the primary crushing, while a In size separation, a sieve is used to classify the different sized
number of mills have been reported for the finer comminution particles. The size of sieve apertures can be varied according to
(Iji and Yokoyama, 1997; Zhang and Forssberg, 1997; Mou et al., the desired particulate size for separation. Screening has not only
2004), with the swing hammer types appearing to have become been utilized to prepare a uniformly sized feed to a certain
the industry standard (Goosey and Kellner, 2003; Sander et al., mechanical process, but also to upgrade metals contents. Screening
E-Waste E-Scrap WEEE
Remove reusable/ hazardous parts

Segragaon / Hand Sorng Plascs steel cables fans
Manual Selecve Disassembly electric motors power supply
CRT glass baeries PCBs
1st Stage Size Reducon

SHREADING
Glass
Physical Separaon Processes
Gravity Separaon Process
Non Metals Plascs Metals
Recyclables Non Recyclables Flame Retardents Ferrous Non Ferrous

PE, PP, PVC Fibers Resins BFR PBB Fe, Ni, Co
PFTE, PPE Epoxy PBDE Steel Hazardous Precious Rear Earth Elements
Naylon Cr, Hg, Cd Au, Ag, Pd Ta, Ga, Te, In
Be, Pb, Zn Pt PGMs
Chemical Pyrolisis Process Incineraon Ni
Depolimerisaon
Magnec Separaon Process

Carbon Furnace Gases Energy
Black/Tar Oil/Fuel Producon
Ferrous Non Ferrous
Fe, Ni, Co
Steel Hazardous Precious Rear Earth Elements
Cr, Hg, Cd Au, Ag, Pd Ta, Ga, Te, In
Be, Pb, Zn Pt PGMs
Pyrometallurgy Ni
Fe and steel blast furnace
Arc furnace, BOF
Fe, steel 2 nd Stage Size Reducon
HAMMER MILLING
Ferrous
Fe, Ni, Co
Steel Magnec Separaon Process
Non Ferrous
Hazardous Precious Rear Earth Elements

Cr, Hg, Cd Au, Ag, Pd Ta, Ga, Te, In
Be, Pb, Zn Pt PGMs
Ni
Eddy Current /Corona Electrostac Separaon Process
Non Metals Non Ferrous Metals

Remaining Plascs Al Cu, Pb, Zn Sb, Bi, Sn
Au, Ag, Pd
Pt
Metallurgical Separaon Processes
Hydrometallurgy Pyrometallurgy Biohydrometallugy

Leaching Smelting Bacteria, Fungus leach
Cu, Pb, Zn, Ni Cu, Pb, Zn, Ni, Sb, Bi, Sn Cu, Ni
H2SO4
Purificaon/Refining
n Electrowinning
Cyanex, Versac,TBP Cu/Zn/Fe powders Purist metals obtained
Cu, Ni, Au, Ag Cu, Au, Ag Cu, Ni, Au, Ag
Fig. 12. E-waste recycling flowsheet with a combination of physical, chemical and metallurgical separation techniques.
is necessary because the particle size and shape properties of met- (ICP–OES), Mass Spectrometer ICP–MS, fire assay, X-ray Fluores-
als are different from that of plastics and ceramics. The primary cence (XRF) and X-ray Diffraction (XRD) (Zhang and Forssberg,
method of screening in metals recovery uses the rotating screen 1997). Generally, spectroscopic techniques; i.e. X-rays, flame,
or trammel. After primary shredding and screening, secondary plasma, infra-red; can give good qualitative information, but for
stage crushing/pulverizing with dry air cyclone classification are quantitative analysis, every source of error (sampling, digestion,
used with dust collection systems. dilution, calibration, interference, etc.) can be of very detrimental
effect with such highly heterogeneous sample (Ogunniyi et al.,
3.4. Chemical composition determination 2009).
The elemental composition of PCBs varies depending on the
Chemical composition and liberation are critical attributes in type of PCBs and its applications. In general, PCBs contain about
characterizing PCBs for beneficiation investigations. No procedural 28% metals, 23% plastics and the remaining percentage as ceramics
standard exists for the determination of its chemical composition, and glass materials (Zhou and Qiu, 2010). The substrate is mainly
or for the 75 lm fines generated during its comminution. made of epoxies or cyanate resins or phenolic resins. Along with
(Ogunniyi et al., 2009). Reviews and investigations on PCBs have the resin, different types of hardener are required for cross-
mentioned techniques such as Atomic Absorption Spectropho- linking to form thermoset plastics. The most commonly used
tometer (AAS), Inductively Coupled Plasma Spectrophotometer hardeners are dicyano diamide, 4.40 -diaminodiphenyl sulfone,
alumina, alkaline and alkaline earth-oxides and small amounts of

other mixed oxides such as barium titanate, are also present.
Ceramic materials such as BeO, glasses can also be found in the
bridges and slots of PCBs. Around 10–20% of the PCB is made up
with Cu, which forms the conducting layer for electrical connection
between different components. Precious metals especially Au and
Pd are used as contact materials in joints. Typical Sn/Pb solders,
which are used for joining different components in PCBs, account
for 4–6% of the total PCB weight. Components that are mounted
on PCBs also contain different metallic values such as Ga, In, Ti,
Si, Ge, As, Sb, Se, Te, and Ta. The PGMs are present in relays,
switches or in sensors (Sum, 1991).
3.5. Gravity separation
Gravity separation is based on the fact that every material par-

ticle has a specific density. Gravity concentration methods separate
materials of different specific gravity by their relative movement in
response to gravity. Nonetheless, this separation is not only depen-
dent on the density of the components, but also on their size.
Besides gravity one or more of the other forces, like force exerted
by the viscous liquid (such as water or air), can serve as the
separation medium. By using different heavy liquids (such as tetra-
bromoethane – TBE), the metals can be separated from the plastics
or ceramics. Water or airflow tables, heavy media separation and
sifting are common gravity separators used in e-waste recycling.
Different metal particles can be further separated. For this purpose,
the PCB material is processed on concentrating tables. The shaking
tables exploit the difference in the specific gravity and particle size
to achieve desired separation. The principle of the air classification
technique is based on the suspension of the particles in a flowing
air stream and the separation of the particles based on their
Fig. 13. PCB material size before and after shredding. density difference. Density separation techniques which are well-
known in the mineral processing industry have found their way
into e-waste recycling based on the fact that electronic scrap con-
sists essentially of plastics, with a density less than 2.0 g/cm3; light
4.40 -diaminodiphenyl methane (Ghosh et al., 2015). The loss-on- metal, primarily Al and glass, with a density of 2.7 g/cm3; and
ignition (LOI) can be used to determine the polymeric fraction heavy metals, predominantly Cu and ferromagnetics, with a den-
(volatile organic materials) and the aqua regia (AR) leaching can sity more than 7 g/cm3. In sink-float separation, both PC and PCB
be used to determine the metal fraction. The ceramic fraction can scraps 50% (weight) of floats which is primarily plastics can be
be calculated by the mass difference (Yamane et al., 2011). separated out at the specific density of 2.0 g/cm3 (Zhang and
The principal reinforcing material for PCB substrate is cloth Forssberg, 1997, 1999). Sarvar et al. (2015) used a jig for +0.59
made of glass fibers or silica. Other inorganic materials such as and 1.68 mm PCB particles.
Fig. 14. Small scale PCB recycling plant layout.

3.6. Magnetic separation hardened plate. Then the small particles, typically less than
0.6 mm are passed along a vibratory feeder to a rotating roll to
Magnetic separation can be used to separate magnetic metallic which is applied a high voltage electrostatic field using a Corona
particles (ferrous) from non-magnetic particles (non ferrous) (i.e. and an electrostatic electrode (Lu et al., 2008; Hadi et al., 2015).
plastics, glass, Al, etc.) Magnetic separators, in particular low- The nonmetallic particles that become charged and attached to
intensity drum separators are widely used for the recovery of fer- the drum eventually falling off into storage bins; whereas the
romagnetic metals from nonferrous metals and other nonmagnetic metallic particles discharge rapidly in the direction of an earthed
wastes. Over the past decade, there have been many advances in electrode.
the design and operation of high-intensity magnetic separators It has been found that particle sizes of 0.6–1.2 mm are the most
(HIMS), mainly as a result of the introduction of rare earth alloy suitable size for separation in industrial applications. Therefore, a
permanent magnets capable of providing very high field strengths two-step crushing process has been proposed to achieve this par-
and gradients. There are some problems associated with this ticle size (Fig. 12). Li et al. (2008) found that as the angle of the sta-
method. One of the major issues is the agglomeration of the parti- tic electrode reduced and the Corona electrode angle was
cles which results in the attraction of some nonferrous fraction increased, the separation efficiency was enhanced. It was reported
attached to the ferrous fraction (Veit et al., 2005). This will lead that applied voltage of 20–30 kV, center distance of 21 cm, static
to the low efficiency of this method. Through the process of mag- electrode radius of 1.9 cm, Corona wire radius of 11.4 cm, static
netic separation, it is possible to obtain two fractions: magnetic electrode angle of 20° and Corona electrode angle of 60° were
fraction, which includes Fe, steel, Ni, etc. and non-magnetic frac- the optimum operating parameters influencing the separation
tion, which includes Cu (Yamane et al., 2011). efficiency. Considerable work is continuing in this area with
Veit et al. (2005) employed a magnetic field of 6000– particular focus on the electrostatic behavior of the system and
6500 Gauss (G) to separate the ferromagnetic elements, such as the field intensity (Hadi et al. (2015). Corona electrostatic methods
Fe and Ni. The chemical concentration of the magnetic fraction are now capable of producing two streams from PCB waste
was 43% Fe and 15.2% Ni on average. However, there was a consid- comprising a metallic and a nonmetallic portion with little cross-
erable amount of Cu impurity in the magnetic fraction as well. Yoo contamination; the method is dry at room temperature and as such
et al. (2009) used a two-stage magnetic separation to milled PCBs. is almost zero polluting depending on the quality of the dust
The milled PCBs of particle size >5.0 mm and the heavy fraction extraction system. The residual Cu metal in nonmetallic fraction,
separated from the <5.0 mm PCBs particles by gravity separation. which were separated from waste PCBs without ECs by using the
In the first stage, a low magnetic field of 700 G was applied which Corona electrostatic separator, showed that most of the residual
led to the separation of 83% of Ni and Fe in the magnetic fraction Cu is in fine size range (7–9 lm) (Guo et al., 2008).
and 92% of Cu in the non-magnetic fraction. The second magnetic Industrial electrostatic separators adopt physical high voltage
separation stage was conducted at 3000 G which resulted in a to separate conductor metals from non-conductor non-metals with
reduction in the grade of the Ni–Fe concentrate and an increase a separation efficiency of 95–99% purity. Electrostatic separator
in the Cu concentrate grade. power changes from 1.5 to 3 kW, rotational speed from 20 to
300 rpm, static electricity from 50,000 to 150,000 V adjustable
3.7. Electrostatic separation (www.alibaba.com/product-detail). Considerable work is continu-
ing in this area with particular focus on the electrostatic behavior
Electrostatic separation separates materials of different electri- of the system and the field intensity.
cal conductivity (or resistivity). There are three typical electric
conductivity-based separation techniques: (1) Corona electrostatic 3.8. Froth flotation
separation, (2) triboelectric separation and (3) Eddy current
separation. The electrostatic separating capability depends on the Exploiting natural hydrophobicity, as well as reverse flotation is
difference in polarity and the amount of charge acquired by parti- quite common in coal and Fe ore flotation, respectively, while some
cles to be separated. Induction or Corona charging can successfully application of flotation has also been reported in waste processing
separate the mixed particles that have large difference in conduc- (Guo et al., 2008). A major challenge to the physical processing
tivities. Tribo-electricity or contact charging is useful for charging alternative is the poor recovery of the base and precious metal
and separating materials that have similar conductivities. The values deported to the 74 lm fine fraction generated during the
principle of Eddy current separation is that in separation zone comminution operation. Assessing this as an applied minerals pro-
gravitational, centrifugal, frictional, and magnetic deflection forces cessing problem, froth flotation has been advanced as a promising
influence the falling particles, but only magnetic force deflects the beneficiation technique for this fine fraction (Iji and Yokoyama,
ferrous particles to a higher degree. To separate ferrous particles, 1997; Ogunniyi and Vermaak, 2007). It is mainly used for drawing
the magnetic deflection force acting on the ferrous particles has back nonferrous metal. The use of froth flotation in environment
to be greater than all competing forces (Li et al., 2004). protection, plastic recycling and sorting were reviewed by Saitoh
Eddy current separation technology is used to recover Al, which et al. (1976), Shent et al. (1999), Dodbiba et al. (2002), Kaya
consists of approximately 2.8% by weight of a typical PCB scrap (2005) and Alter (2005). Sarvar et al. (2015) used mechanical
(Guo et al., 2008). Eddy current separators can remove Cu, Al, separation from computer PCBs with jigging (for +0.59 to
nonferrous metal scrap, broken glass, etc. Al fraction is sent to alu- 1.68 mm size) and flotation (for 0.59 mm size). Collectorless
minum smelter for further treatment. The Corona-electrostatic flotation with gasoline was promising method for separating non-
method is perhaps the most effective separation technology for metals (i.e. polymers) of PCBs. 85% metal recovery from flotation
the metallic and non-metallic fractions at present. The method and more than 95.6% metal recovery from jigging were obtained
has the advantage of being environmentally friendly, producing but,4.95% Cu and 24.5% Au were lost during concentration.
no wastewater and no gaseous emissions. In the Corona-
electrostatic separation, electrode system, rotor speed, moisture 3.9. Perspectives of physical recycling
content and particle size have the greatest effect in determining
the separation results. The PCBs with the metallic components Physical recycling of metallic and nonmetallic fractions is
removed must be reduced to very small particles which can be adopted in mechanical recycling of waste PCBs. Mechanical pro-
achieved by accelerating them at high speed to impact on a cesses, such as screening, shape separation, magnetic separation,
Eddy current separation, electrostatic separation and jigging have to recover metals and pyrolysis gas was reused as fuel gas in the
been widely utilized in recycling industry. The basic topic in non- process.
metallic fraction recovery by physical separation is how to use Representative starting temperature of pyrolysis on PCB waste
these recovered materials as effective, cheap and safe filler for reveals that 270–280 °C is the critical temperature to produce
different materials. Nonmetallic fraction materials are diverse, gases pollutants (Duan et al., 2011). Combustion recycles the
complex and toxic. calorific value of thermoset resins directly; but, converts glass
The advantages of physical recycling methods are that the pro- fibers to a glass-slag which significantly reduces the combustion
cessing is relatively simple, convenient and environmentally efficiency. Evangelopoulos et al. (2015) investigated the thermal
sound, the initial equipment investment and energy cost are low decomposition of PCBs via TGA and analytical pyrolysis at a tem-
and potential application of products is diversified. There are still perature range of 400–900 °C. They found that the main decompo-
some challenges in physical separation between the metallic and sition of PCBs occurs between 250 °C and 370 °C. 79% w/w ash
nonmetallic fractions from waste PCBs. Significant dust generation content with metals and ceramic materials were obtained along
and metal loss during shredding and grinding are some important with aromatic compounds. Vats and Singh (2015) assessed the
drawbacks of the process. Prevention of hazardous substances Au and Ag in assorted mobile phone PCBs by subjecting them to
from leaching out of products made from recycled materials and roasting at 850 °C and HCl acid digestion. They found that the
persuasion of public to uses the recycled products that have passed existence of precious metals Au and Ag in mobile phone PCBs in
the relevant environment safety tests are serious challenges. the portion of 1:25–1:47. Au and Ag are available in the range of
Today, Chinese and Japanese recycling facilities generally use dis- 0.009–0.017% and 0.25–0.79% respectively.
mantling and mechanical processing of e-waste for the recovery
of raw materials. Process flowsheets include manual selective 4.1. Perspectives on chemical recycling of the nonmetallic fractions
disassembly, shredding, magnetic and electrostatic Eddy current from PCBs
separations (Tsydenova and Bengtsson, 2011).
The main purpose of chemical recycling processes is to convert
4. Chemical recycling techniques the polymers to chemical feedstocks or fuels. Compared to physical
recycling methods, chemical recycling methods have the advan-
Chemical recycling is to decompose the waste polymers into tages in converting BFRs to monomers and in taking out the heavy
their monomers or some useful chemicals by means of chemical metals left in residue. It is possible to prevent formation of dioxins
reactions. Pyrolysis, gasification, depolymerization using supercrit- and furans by adding CaO in the pyrolysis of the waste PCBs.
ical fluids and hydrogenolytic degradation processes are four Practical usage of produced oil will be expensive as compared to
chemical recycling techniques (Guo et al., 2009). Chemical recy- petrochemical oils. However, chemical recycling of nonmetallic
cling separates organic and metallic materials. Many chemical fractions is the most effective method to take full advantage
recycling processes of waste PCBs have been tested in a laboratory of all the valuable elements and remove all the hazardous and
scale. For instance, the pyrolysis process (heating without oxygen) toxic components contained in the nonmetallic fractions (Duan
was employed to obtain high purity metals. PCB nonmetallic resin et al., 2011).
fraction decomposes to its original constituents. Uncertainty and
potential pollution have declined the process to expand into a field
scale (Zeng et al., 2012). Pyrolysis involves the destructive distilla- 5. Metallurgical processes
tion of resin from a range of polymer types. During pyrolysis
process, the organic materials were decomposed to low molecular Metallurgical processes are used in the upgrading and refining
weight products, liquids/oils/tars or gases which can be used as stages of the recycling chain. In metallurgical processes, metals
fuel, while the inorganic components (mainly metals and glass are melted by heat (pyrometallurgical processes) or dissolved by
fibers remained as solid residue relatively unaltered and, therefore, a liquid (hydrometallurgical processes) and further sorted by mak-
can be recycled in worthwhile application. Resin solid product is ing use of their chemical/metallurgical properties. Pyrometallurgi-
char and low value. The obtained products are refined by conven- cal processing, notably smelting, has become a traditional method
tional approaches and the metallurgical approaches are employed to recover metals from e-waste in the last three decades. In
for the treatment of the metallic fraction. A major shortcoming is hydrometallurgical treatment, the main steps are acid, cyanide or
the presence of the significant amount of dioxin precursors in caustic leaching of solid material. From the solutions, the metals
pyrolysis oils, which can possibly be reduced by adding CaCO3 of interest are then isolated and concentrated. Leaching solvents
and Fe2O3 during pyrolysis. In recent years, supercritical fluids are H2SO4-H2O2, aqua regia (AR), thiourea, cyanide, HNO3, NaOH,
have been an effective medium for the destruction of epoxy adhe- HCl, etc. (Tsydenova and Bengtsson, 2011).
sive layer.
Centrifugal separation (N: 1400 rpm and t: 6 min) and vacuum 5.1. Pyrometallurgical processes (smelting)
pyrolysis processes (P: 1.5 kPa, T: 600 °C, t: 30 min) were tested in
laboratory scale to separate solder and organic materials from PCBs Pyrometallurgy, energy intensive and high-cost process, is the
(Zhou and Qiu, 2010). This method claimed two advantages of traditional approach for metal recovery from the waste PCBs;
short organic vapor residence time in the reactor and low decom- but, selective recovery of individual metals can hardly be done
position temperature which reduces the occurrence and intensity by this route. Pyrometallurgical techniques include incineration,
of secondary reactions. In this two-step process, firstly, solder smelting in plasma arc furnace, blast furnace or Cu smelter, high
was melted in the heated dieseloil + molten solder and some ECs temperature roasting in presence of selective gases to recover
were removed by centrifugal separation and then desoldered PCBs mainly nonferrous metals. (Kaya, 2009, 2016b). Currently, more
were subjected to the vacuum pyrolysis to obtain pyrolysis oil and than 70% of waste PCBs is treated in smelters rather than through
gas and pyrolysis residue (includes base plates and ECs). Recovered mechanical processing (Cui and Zhang, 2008). The main advantage
solder can be reused directly and it can also be a good resource of of pyrometallurgical treatment is its ability to accept any forms of
Pb and Sn for refining. The chemical properties of the recovered scrap. Hence, electronic scrap can be used as a part of raw materi-
solder remained unchanged, because the PCBs were immersed into als in the smelters for recovery of Cu along with Au and Ag
oil during the process. This residue was sent for further treatment (Sum, 1991). However, the pyrometallurgical methods have some
Fig. 15. Pyrometallurgical recycling process of e-waste and Cu concentrate (https://www.emaze.com/@AOCLCZRT/Smelting-presentation-JD.pptx).
disadvantages such as generation of large amount of slag, loss of swelled). It is easier to control over reaction and creates less
precious metals and difficulty in recovery of Al and Fe and other environmental hazards than pyrometallurgical approach. The base
metals (Cui and Zhang, 2008). A recycling method, developed by metals recovery has a substantial impact on the economics of the
Berlin Technical University in 1997, turned waste PCBs into a process due to larger available amount in waste PCBs. Moreover,
Cu-Ni-Si alloy, a mixed oxide (mainly Pb and Zn) and environmen- recovery of base metals also ensures the enrichment of precious
tally agreeable slag by a top blown reactor (Bernardes et al., 1997; metals in the solid residue, making it easier to leach out subse-
Shrivastava et al., 2004). Vacuum metallurgy separation (VMS) is quently (Ghosh et al., 2015). Low capital cost hydrometallurgical
suitable for Bi, Sb, Pb and other heavy metals with high vapor pres- processes are mainly used for recycling of the metallic-ferrous
sure. At Boliden Ltd. Ronnskar Smelter in Sweden, waste PCBs are fraction where the extraction of the metal content is profitable.
directly fed into Cu converter to recover Cu, Ag, Au, Pd, Ni, Se Depending on the substrate material (ceramic, glass, or polymer),
and Zn; while the dust containing Pb, Sb, In and Cd is processed there are different hydrometallurgical processes used (Li et al.,
separately for metal recovery (Theo, 1997). At Umicore’s integrated 2004). In hydrometallurgical processes, a large amount of liquid
metal smelter and refinery, electronic scraps are first treated in wastes and sludge are produced and must be disposed carefully.
IsaSmelt furnace to recover precious metals along with Cu in the A slow leaching kinetic is another drawback of the process.
form of Cu-bullion. Cu is first recovered from this bullion through Electro-oxidation can reduce the acid consumption amount and
Cu leaching and electrowinning followed by precious metals recov- recover valuable metals without loss.
ery from Cu-leached residue in precious metal refinery (Hagelüken,
2006). Fig. 15 shows a general flowsheet for Cu recovery as Cu 5.2.1. Precious and base metal recoveries by acid/alkaline leaching
cathode from waste electronic equipment by a pyrometallurgical Currently, around 300 tons of Au are used in electronic indus-
route combined with electrolysis (Antrekowitsch et al., 2006; tries along with other precious and strategic metals like Ag, Pd,
Gramatyka et al., 2007; Kaya, 2009). Pt, Nb, Ta, etc. (Montero et al., 2012). Most of the precious metals
Pyrometallurgical treatment generates fumes of heavy metals are present in elemental form and in proximity of other metals,
(especially low melting point metals such as Hg, Pb, and Cd). which makes very difficult to separate the individual ones
Besides, if the feedstock contained PVC or other plastics with BFRs, (Ghosh et al., 2015). To improve the selectivity of the precious met-
pyrometallurgical treatment may lead to the formation of mixed als and minimize the impurities, leaching is preferably carried out
halogenated dioxins and furans. after the removal or recovery of base metals. Sheng and Etsell
(2007) in sequential steps first dissolved the base metals in
5.2. Hydrometallurgical processes (leaching) HNO3, followed by leaching of the first step leach residue in AR
to extract Au and finally precipitation of Au with ferrous sulfate.
Hydrometallurgical route is more selective towards metal Nevertheless, the construction of the leaching reactor suitable for
recovery from waste PCBs or pretreated PCBs (desoldered or highly corrosive HNO3 and AR, limits its industrial feasibility.
Table 6
Precious metal leaching reagents, reactions, conditions, advantages and disadvantages (Kaya, 2016a).
Lixiviant Cyanide Thiourea Thiosulfate Potassium persulfate Halide

Reagent CN, O2 (air) SC(NH2)2, Fe3+ S2O2
3 , NH3, Cu
2+
2[SO4] Chlorine/chloride Cl/Cl2
KCN CH4N2S (NH4)2S2O3 K2S2O8 NaCl, hypochlorite, HCl, HClO4, NaClO
65.12 g/mol 76.12 g/mol Na2(S2O3)5H2O hypo 270.322 g/mol Iodide I/I2
1.52 g/cm3 1.405 g/mL 158.11 g/mol 2.477 g/cm3 KI
71.6 g/100 mL (25 °C) 14.2 g/100 mL (25 °C) (anhydrous) 4.49 g/100 mL (20 °C) Bromide Br/Br2
NaCN 248.18 g/mol
49.10 g/mol (pentahydrate)
1.596 g/cm3 1.667 g/cm3
63.7 g/100 mL (25 °C) 70.1 g/100 mL (20 °C)
M. Kaya / Waste Management 57 (2016) 64–90

Reactions 4Au + 8CN + O2 + 2H2O ? 2Au + 4CS(NH2)2 + 2Fe3+ M 4Au + 8S2O2
3 + O2 + 2H2O ? 4Au Dissolve all base metals 2Au + 11HCl + 3HNO3 M
4Au(CN)2 + 4OH

2Au(CS(NH2)2)+2 + 2Fe2+ (S2O3)3
2 + 4OH

retaining only gold in solid 2HAuCl4 + 3NOCl + 6H2O
residue
Species and Au(CN)
2 (log K: 38.3) Au(CS(NH2)2)+2 (log K: 22) Au(S2O3)3
2 (log K: 28.7) AuCl4 (log K: 29.6)
their stability Ag(CN)
2 (log K: 20.3) Ag(CS(NH2)2)+2 (log K: 13) Ag(S2O3)3
2 (log K: 13)
Conditions E°: 0.67 V, pH > 10, 25 °C E°: 0.38 V, pH: 1–2, 25 °C E°: 0.274–0.038 V, E°: 1.0 V, pH < 4, 25 °C
pH > 8–11, 25 °C
References Montero et al. (2012) Ficeriova et al. (2008) and Oh et al. (2003) Syed (2006) Quinet et al. (2005)
Results Column leaching of crushed PCBs: 46.4% Ficeriova et al. (2011) 0.2 M (NH4)2S2O3 99.5% Au with melting Oxidative leaching using HNO3 or H2O2 in
Au, 51.3% Ag, 47.2% Nb, 62.3% Cu Crushed PCBs,10 g/L H2SO4 and 0.02 M CuSO4 chloride medium (HCl and NaCl), 75 °C
CS(NH2)2 5 g/L ferric sulfate, 2 h 0.4 M NH4OH 93–95% Pd
90% Ay, 68% Cu, 45%Fe, 43%Pb 400 °C, 48 h
and 28% Zn 95% Au, 100% Ag
References Quinet et al. (2005) Behnamfard et al. (2013) Ha et al. (2010) Xu et al. (2010)
Results Bench scale, PCBs 20 g/L CS(NH2)2 0.12 M (NH4)2S2O3 Iodide leaching
1. Oxidative H2SO4 leach to 6 g/L 5 g/L ferric sulfate 20 mM CuSO4 1–1.2% iodide conc.
dissolve Cu and Ag 10 g/L H2SO4 0.2 M NH4OH 1–2% H2O2
2. Oxidative chloride leaching S/L: 1/10 (g/mL) 2 h 98% Au PCB S/L: 1/10
to dissolve Pd and Cu Ambient temp., 3 h 10 h 90% Au mobile phone pH: 7
3. Cyanide leaching Au, Ag and Pd 85.76% Au, 71.36% Ag Ambient temp., 4 h
95%Au, 93% Ag and 99% Pd 95% Au
Commands Toxic and have serious environmental Non-toxic, non-corrosive, Oxygen carrying catalyst Non-toxic, strong oxidizing Non-toxic, non-corrosive, very selective.
Ads/Pros issues less environmental impact. Cost and Cu(NH3)2+
4 is required agent Consumption, reagent cost, chlorine gas,
consumption important factors Non toxic and special reactor requirement
non-corrosive
81
Table 7
82
Base metal leaching reagents, reactions, conditions, advantages and disadvantages (compiled from Kaya, 2016b).
Lixiviant H2SO4 + (H2SO4 + H2O2) H2SO4 + H2O2 H2SO4 + H2O2 H2SO4 + H2O2 H2SO4 + H2O2
Reagent First stage: H2SO4 1 M 1/10 w/v 2 M 100 mL H2SO4 + 20 mL 30% H2O2 2.5 M H2SO4 + 20% H2O2 + super critical 2 M H2SO4 H2SO4 (15%) + H2O2 (30%) + 10 g/L
Second stage: H2SO4 1 M 1/10 w/v CO2(g) initial Cu ion
+ 240 mL H2O2
Reactions H2O2 + 2H+ + 2e ? 2H2O H2O2 + 2H+ + 2e ? 2H2O H2O2 + 2H+ + 2e ? 2H2O
Cu + H2SO4 + H2O2 ? CuSO4 + 2H2O Cu + H2SO4 + H2O2 ? CuSO4 + 2H2O Cu + H2SO4 + H2O2 ? CuSO4 + 2H2O
Zn + H2SO4 + H2O2 ? ZnSO4 + 2H2O Zn + H2SO4 + H2O2 ? ZnSO4 + 2H2O Zn + H2SO4 + H2O2 ? ZnSO4 + 2H2O
Sn + H2SO4 + H2O2 ? SnSO4 + 2H2O Sn + H2SO4 + H2O2 ? SnSO4 + 2H2O Sn + H2SO4 + H2O2 ? SnSO4 + 2H2O
Fe + H2SO4 + H2O2 ? FeSO4 + 2H2O Fe + H2SO4 + H2O2 ? FeSO4 + 2H2O Fe + H2SO4 + H2O2 ? FeSO4 + 2H2O
Ni + H2SO4 + H2O2 ? NiSO4 + 2H2O Ni + H2SO4 + H2O2 ? NiSO4 + 2H2O Ni + H2SO4 + H2O2 ? NiSO4 + 2H2O
Species and DG = 77.941 kcal/mol (Cu) DG = 77.941 kcal/mol (Cu) DG = 77.941 kcal/mol (Cu)
their stability DG = 127.965 kcal/mol (Zn) DG = 127.965 kcal/mol (Zn) DG = 127.965 kcal/mol (Zn)
DG = 136.895 kcal/mol (Sn) DG = 136.895 kcal/mol (Sn) DG = 136.895 kcal/mol (Sn)
DG = 115.847 kcal/mol (Fe) DG = 115.847 kcal/mol (Fe) DG = 115.847 kcal/mol (Fe)
DG = 101.244 kcal/mol (Ni) DG = 101.244 kcal/mol (Ni) DG = 101.244 kcal/mol (Ni)
Conditions 75 °C, 4 h 50 °C, 3 h, pH: 1.48–1.52 S/L: 1/20, 35 °C,600 rpm, 60–240 min, 85 °C, 12 h 23 °C, 3 h
PCBs (3 mm) 2 mm, atm. pressure PCBs (1.0 mm)
References Silvas et al. (2015) Birloaga et al. (2013) Calgaro et al. (2015) Oh et al. (2003) Yang et al. (2011)
Results 46.3% Cu, 5.7% Fe, 21.1% Sn, 51.1% Zn pH: 90% Cu 100% Cu and Zn, 95% Fe, Ni >90% Cu
1.48 and Al
M. Kaya / Waste Management 57 (2016) 64–90

11.5% Cu, 62.2% Fe, 26.4% Sn, 31.8% Zn
pH: 1.52
Commands H2O2 environmentally friendly and Oxidant CO2 fastens kinetics, reusable
Ads/Pros oxidant and environmentally acceptable
Lixiviant H2SO4 + Cu2+, Cl + O2 (CuSO4-NaCl) H2SO4 + H2O2 HNO3 + organic swelling (n-methyl-2- HNO3
pyrrolidone)
Reagent 0.5 M H2SO4 + 0.5 g/L Cu2+, 25.6 g/L Cl + O2 > 2 g/ 2 M H2SO4 + 35% H2O2 (1st step leach) 0.2 M HNO3 for Pb leach 1–6 M HNO3 + electrodeposition
L 2 M H2SO4 + 35% H2O2 (2nd step leach) 3.5 M HCl for Sn leach
Reactions Pb(s) + 2HNO3 ? PbO(s) + H2O + NO2(g) 3Cu + 8HNO3 ? 3Cu(NO3)2 ? 4H2O + 2NO
PbO(s) + 2HNO3 ? Pb(NO3)2 + H2O Pb + HNO3 ? Pb(NO3)2 + H2
Sn + 4HNO3 ? H2SnO3(s) + 4NO2 + H2O
Ni + 4HNO3 ? Ni(NO3)2 + 2NO2 + 2H2O
3Zn + 8HNO3 ? 3Zn(NO3)2 + 4H2O + 2NO
Conditions 80 °C, 2 h 25 °C, 3 h S/L: 1/100 gr/mL, 90 °C, 45 min for Pb 23–80 °C, 23–80 °C, 15–360 min
S/L: 1/20 gr/mL, 90 °C, 2 h for Sn PWBs shredding, S/L: 1 g/3 mL
References Yazıcı and Deveci (2013) Behnamfard et al. (2013) Jha et al. (2012) Mecucci and Scott (2002) and Kinoshita et al. (2003)
Results 100% Cu 85.76% Cu (1st step) 99.99% Pb, 98.74 Sn 90% Pb 4 M HNO3, 60 min, 80 °C, 83%
13.99% Cu (2nd step) Cu 4 M HNO3, 60 min, 80 °C
Pb and Cu > 90%, H2SnO3 (;)
Commands Ads/ Pb and Cu are easily dissolved. Precipitated
Pros Sn is dissolved by HCl later
Lixiviant HBF4 + H2O2 Ammonia-ammonium sulfate HNO3 HCl

Reagent 2.5 M HBF4 + 0.4 M H2O2 2 M NH3 + 2 M (NH4)2SO4 + SX (LIX 84 + kerosene) 2–5 M HNO3 5.5 M HCl (solder leach) + precipitation
Reactions 2H2O2 + Sn + Pb + 4H+ = Sn2+ + Pb2+ + 4H2O Sn + HCl ? SnCl4 + H2(g)
Pb + 4 HCl ? H2[PbCl4] + H2
Conditions 35 min, 20 °C 35 °C, 400 rpm, 2 h, 12 m3/h air, S/L: 1/10 g/cm3 30–70 °C, 120 min, pulp density: 2–10% w/v, 350 rpm 165 min, 50 g/L, 90 °C
Scrap TV boards (250 lm)
Currently, the active research has been shifted towards the devel-
Aspergillus niger, Penicillium simplicisimum

opment of less corrosive reagents such as cyanide, halide, thiourea,
99.90% Pb 0.1 M HNO3, 90 °C 10 g/L
97.79% Sn, 4.5 M HCl, 60 min, 90 °C
potassium persulfate and thiosulfate for precious metals leaching

from waste PCBs (Ghosh et al., 2015). Table 6 summarizes precious
metal leaching reagents, reactions, results, conditions, advantages
65–95% Cu, Sn, Al, Ni, Pb, Zn

and disadvantages along with references. Au leaching by cyanide
follows the following reactions:
Brandl et al. (2001)
Jha et al. (2012)
4Au þ 8ðK=NaÞCN þ O2 þ 2H2 O ! 4ðK=NaÞ½AuðCNÞ2 þ 4ðK=NaÞOH

ð1Þ
Overall : 4Au þ 8CN þ O2 þ 2H2 O ! 4AuðCNÞ2 þ 4OH ð2Þ
E-waste
In recent years, the recovery of Au by thiourea has gained

worldwide attention due to its less environment impact. Unlike
cyanide, thiourea forms a cationic complex with Au in acidic med-
ium and can dissolve up to 99% Au as per the following reaction:
Au þ 2CSðNH2 Þ2 ! AuðCSðNH2 Þþ2 þ e ð3Þ

Desulfovibrio desulphuricans
1–2 M H2SO4 along with Fe2(SO4)3, O2 and H2O2 as an oxidant/

reductant were tested in base metal leaching at 50–85 °C for
Creamer et al. (2006)
3–12 h period. 6 M HNO3 at 80 °C for 6–24 h were also tested.

68–95% Au and Pb
88.5–99.9% Cu, 16–68% Ag
H2SO4 + H2O2 achieved better metallurgical performance than

HNO3 alone. Table 7 summarizes base metal leaching reagents,
reactions, results, conditions, advantages and disadvantages along
E-waste
Bas et al. (2014)
with references. Previous studies, given in Table 7, achieved

86–99.5% Au, 71–93% Ag and 93–99% Pd recoveries. H2SO4 + H2O2;
H2SO4 + CuSO4 + NaCl; HNO3; HCl; HBF4 + H2O2; and NH3 + (NH4)2SO4
were used as leaching reagents. Fe2(SO4)3, O2(g) and H2O2 are
potential oxidants for Cu in the following ways:
Cu þ Fe2 ðSO4 Þ3 ! CuSO4 þ 2FeSO4 ð4Þ

Cu þ H2 O2 ! CuSO4 þ 2H2 O ð5Þ
Sulfobacillus thermosulfidooxidans
81% Ni, 89% Cu, 79% Al, 83% Zn
Cu þ 1=2O2 ! CuSO4 þ H2 O ð6Þ

45 °C, 18 d, pH: 2.0, 180 rpm
H2O2 is expensive; but, gives high Cu and Ag recoveries as com-

Ammonia leaches both Cu and Zn
99.6% Cu from SE (pH: 10, 3 min)
pared to O2 and Fe2(SO4)3. Cl2(g), Cu2+, Cl and super critical CO2(g)
PCBs (50–150 lm)
Scrap conc: 10 g/L
Ilyas et al. (2007)
were also tested as reductant for metals recovery from e-waste.

Kim et al. (2011) investigated leaching kinetics of Cu from waste
PCBs by electro-generated Cl2(g) in HCl solution. Leaching up to
96.7% Cu from leach
71% Cu along with 98% Zn, 96% Sn and 96% Pb were achieved using
Yang et al. (2012)
2.0 M HCl solution at 50 °C, 400 rpm and 4 h. Calgaro et al. (2015)
studied fast Cu extraction from old mobile phone PCBs using
supercritical CO2(g) with H2SO4 + H2O2 as co-solvent. The presence
of 20% H2O2 in 2.0–2.5 M H2SO4 mixture led to 87.35% and 88.79%
Cu dissolutions, respectively in 20 min.
Jha et al. (2012) leached Pb and Sn from solder material of waste
Burning at 900 °C, 80 °C, 3 h, <8 mm
PCBs after organic swelling using n-methyl-2-pyrrolidone at 0.2 M

HNO3. Without PCB swelling pretreatment, 99.99% Pb leaching
recovery with 0.2 M HNO3 concentration, 90 °C temperature and
Solder is dissolved, Cu and other
120 min leaching time was obtained. Swelled PCBs achieved the
same Pb leaching under the same conditions at 45 min. 98.74% of
metals are not dissolved
Havlik et al. (2010)
Sn left in residue as H2SnO3; was further leached with 3.5 M HCl

at 90 °C for 120 min at S/L ratio 1:20 (g/mL). Jha et al. (2012) inves-
Zhang et al. (2015)
Pb and Sn dissolve
tigated the leaching of Sn from waste PCB solders. They found that
Cu precipitate
95.79% of Sn was leached out using 5.5 M HCl at 50 g/L pulp den-
>90% Cu
1 M HCl
sity and 50 °C temperature in 165 min mixing time without

HCl
organic swelling pretreatment. However, the same Sn recovery

was found with 4.5 M HCl at 90 °C, mixing time 60 min and pulp
density 50 g/L. The Pb from leach residue was removed by using
Commands Ads/Pros
0.1 M HNO3 at 90 °C in mixing time 45 min and pulp density

10 g/L. Organic swelling of solder from PBCs liberates both Cu lay-
ers and solder material from epoxy resin and increases dissolution
References
References
Conditions
kinetics.
Lixiviant
Reagent
Results
Results
The component reuse oriented disassembly technology for PBCs

offers a novel way for selective solder dissolution to prevent the
environmental pollution effectively. Desoldering separation of
waste PBCs is a key step to recycle or dispose the e-waste effec- Faramarzi et al., 2004; Karwowska et al., 2014). Brandl et al. (2001)
tively. Zhang et al. (2015) studied a new way for selective desolder- indicated that it is possible to mobilize metal from e-waste by the
ing separation using 2.5 M HBF4 + 0.4 M H2O2 at 35 min. use of the microorganisms such as bacteria (Thiobacilli) and
Mecucci and Scott (2002) studied the leaching and electro- fungi (A. niger, P. simpli-cissimum). Faramarzi et al. (2004) used
chemical recovery of Cu, Pb and Sn from scrap PCBs using 1–6 M different cryogenic bacterial strains (Chromobacterium violaceum,
HNO3. They dissolved Cu and Pb very effectively and precipitated Pseudomonas fluorescents, Bacillus megaterium) to recover Au from
Sn as stannic oxide (H2SnO3). Later Sn was leached with 1.5 M waste PCBs and found maximum 14.9% Au dissolution as
HCl and electrodeposited. Both HNO3 and HCl were regenerated dicyanoaurate [Au(CN)2]. An investigation on the extraction of Cu
for reuse. Yang et al. (2012) investigated the recovery of ultrafine from waste PCBs using bacterial consortium enriched from natural
Cu particles from metal components of waste PCBs using a com- acid mine drainage establishes that extraction of Cu is mainly
bined ammonia leaching and solvent extraction process. They accomplished indirectly through oxidation by Fe3+ ions generated
achieved 96.7% Cu recovery at a temperature of 35 °C for a leaching from Fe2+ oxidation by bacteria (Xiang et al., 2010). The Cu recov-
time of 120 min. Ammonium sulfate and ammonia concentration ery rate primarily depends upon the initial pH, Fe2+ concentration
were 2 M at a S/L ratio of 1:10 g/cm3. 99.6% Cu recovery was and bio-oxidation rate of Fe2+. The sequential reactions are (Kasper
achieved using 50% LIX 84 in kerosene at 3 min and pH: 10. et al., 2011);
Silveira et al. (2015) developed a complete process for recover-
ing indium (In) from LCD screens on discarded mobile phones after 4Fe2þ þ O2 þ 4Hþ ! 4Fe3þ þ 2H2 O ð7Þ
3þ 2þ 2þ
removing the polarizing film pretreatment. They used 1.0 M H2SO4, Cu þ 2Fe ! Cu þ 2Fe ð8Þ
1:50 S/L ratio, 90 °C, 1 h and 500 rpm to obtain 613 mg of In/kg of
LCD powder. 99.8% indium precipitated with NH4OH at pH 7.4. Toxic influence of ingredients on the growth of micro-
Jiang et al. (2012) claim the development of a novel process organisms and slow reaction rate are some of the major drawbacks
based on green chemistry and engineering methodologies for projected by various researchers during bioleaching of PCB scrap
reclaiming valuable metals from waste PCBs and ICs. Their (Brandl et al., 2001; Cui and Zhang, 2008; Xiang et al., 2010;
patented eVolvTM process include both chemical desoldering Ghosh et al., 2015).
(10–20 min at 35 °C) and precious metal leach (5–10 min at
30 °C) recovery at near room temperature using cost-effective, sus- 6. Purification
tainable and scaleable methods. Desoldering chemistry is highly
selective towards Pb/Sn and Sn/Ag solders leaving Cu, Ag, etc. on Metals from PCBs are dissolved on leaching process and can
the board and base metals intact. Pb, Sn and Ag salts (typically oxi- be recovered by purification techniques such as: liquid/liquid
des) are recovered in high purity (>95% recovery) and are sold. extraction (solvent-extraction), precipitation/cementation and
From solder free bare PCBs, Au, Ag, Pd, etc. can be leached with electrolyte refinement (electrowinning/electro-recovery) (Lister
99.9% efficiency and >99.9% purity via chemical reduction or elec- et al., 2014; Silvas et al., 2015). Cu can be extracted using LIX 84-
trowinning. For Cu recovery H2SO4 + H2O2 and ammonia; for Pb Kerosene. Direct solvent extraction (DSX) or synergistic solvent
recovery HNO3 and for Sn recovery HCl were best leaching solvents extraction (SSX) can be carried out using Cyanex 301, 302 or 272
in the previous studies. Organic swelling of PCB significantly type lixiviates along with kerosene and TBP for Ni > Co extractions.
increases the leaching kinetics of the metals. Versatic 10, which is neodecanoic acid, TBP and ShellSol 2046 can
be used in Cu/Ni separation or Ni extraction. Extraction, scrubbing
5.2.2. Biohydrometallurgical leaching processes and stripping steps are performed for a compound or metal pro-
Although predominantly targeting the valuable metal fraction duction. Electro-chemical metal extraction route, on the other
recovery from waste PCB, bioleaching could benefit the materials hand, is considered as more environment friendly than chemical
recovery from e-waste in two ways. The use of microorganisms leaching because it involves on the electron transfer process aided
to extract metals by generating weaker organic acids will save on by the supplied electrode potential with minimum chemical
the manufacture of the currently used strong inorganic acids for reagents requirement. Aqueous processing route mostly generates
metal leaching and also save the environment significantly in multi-metal containing solutions and recovery of individual metal
terms of treating and disposing of strong inorganic acid waste either in metal form or as salt is a challenging task. Cementation of
compared to the weaker and more readily treatable organic acids Cu can be achieved by NaCl at 55 °C for 15 min. Cementation of Au/
generated by the microorganism cultures. Bioleaching has consid- Ag from H2SO4 or chloride leach solutions using Cu/Zn/Al powders
erable potential to offer by selectively extracting the metals at low at 60–70 °C for 30–60 min are well known process now. Pd from
temperatures by microorganism and also leaves an unpolluted chloride solution can be best cemented by Al rather than Amberlite
nonmetallic residue for further processing. Biohydrometallurgical IRA68/400, Cu or activated carbon. Cu solvent extraction followed
processing is well established as an alternative route for recovering by Cu electrowinning processes are no doubt established, but
metals especially Cu and Au from very low-grade ores and concen- issues regarding other metals recovery from the PCB leach liquor
trates. The investigations have also been extended to other metals are still unresolved. Au/Ag can also be recovered by activated
due to low investment cost, less environmental impact, less energy carbon adsorption and pyrometallurgy. Fig. 16 shows Hoboken
consumption and better control than the conventional pyrometal- integrated smelter and refinery plant flowsheet of Umicore. This
lurgy or hydrometallurgy routes (Brierley and Brierley, 2001; Cui plant includes Cu-smelter, lead blast furnace, Cu, Pb (Sn, Bi and
and Zhang, 2008). Sulfo-bacillus thermosulfidooxidans achieved Sb), Ni (As), precious (Au, Ag, Pt, Pd, Rh, Ru and Ir) and special met-
81% Ni, 89% Cu, 79% Al, 83% Zn recovery in 18 days at 45 °C with als (In, Te, Se) refineries along with sulfuric acid plant.
PCBs (Ilyas et al., 2007) (Table 7). There is very extensive research A complete motherboard, plastic Central Processing Unit (CPU)
currently being undertaken in bioleaching as it has implications far and ceramic CPU recycling plant flowsheet for recovering Al, Fe, Cu,
beyond treating waste PCBs, including, the mining industry and the Ni, Au, Ag, Pd, Pt and plastic is shown in Fig. 17. This flowsheet
treatment of other wastes containing metals. includes hammer milling, physical separations, leaching, elec-
In recent years, biohydrometallurgy has also been applied for trowinning and waste water neutralization steps.
metal recovery from waste PCBs. The extraction of metals such Biosorption, another facet of biohydrometallurgy, is a procedure
as Cu, Ni, Zn, Cr and precious metals from PCB scrap is technically to recover metals from the leach liquor. The procedure is based on
feasible by the use of bacteria-assisted reaction (Brandl et al., 2001; the different physicochemical interactions (such as ion exchange,
Fig. 16. Flowsheet of Umicore-Hoboken integrated smelter and refinery plant (reprinted with permission from Acta Metallurgica Slovaca (AMS), 2006).
complexation, coordination and chelation) between metal ions and PP resin matrix composites as filler was optimum (Guo et al.,
the charged surface groups of microorganisms (Ghosh et al., 2015). 2009; Biswal et al., 2015).
The nonmetallic fractions (shredded PCBs as a coarse aggregate)
can also be used with some effectiveness as a partial replacement
7. Alternative uses of nonmetallic fraction of inorganic aggregates in concrete applications to decrease the
dead weight of structures and increase properties of concrete such
In fact, most of the researchers recycle the nonmetallic fractions as compressive strength, splitting tensile strength, modulus of
as filler for thermosetting resin composites and thermoplastic resin elasticity, impact resistance, permeability and abrasion resistance.
composites when considering physical recycling methods. Physical Lightweight concrete can be produced from waste thermoset
recycling grinds nonmetals into fine particles for addition into new resins which also improve compressive and flexural strength of
composites as filler if they are clean. The nonmetallic powder concrete if they are mixed in proper ratio (Guo et al., 2009).
obtained from mechanical process can only be used as low-value From the environmental protection and resource saving view-
product (i.e. paint, paving material, cement, plastic and asphalt fill- points, the asphalt modification with the nonmetallic fraction is
ing material) (Zhou and Qiu, 2010). The milled PCB particles of reasonable and significant. Currently most of the nonmetallic frac-
<5.0 mm were separated into a light fraction of mostly nonmetallic tions are subjected to landfilling, incineration and open dumping
components and a heavy fraction of metallic components by causing potential threat to the environment as well as loss of
gravity separation using a zigzag classifier (Model 1-40 MZM, resources (Guo et al., 2009; Ghosh et al., 2015). In summary, phys-
Hosokawa Alpine Ag) (Yoo et al., 2009). ical recycling process for recovery of nonmetallic is much more
The addition of nonmetallic fractions to concrete can enhance advantageous than chemical recycling as the former is relatively
the engineering properties of concrete such as strength, durability, convenient and environment friendly, equipment and environment
shrinkage and permeability. From industrial application viewpoint, control measures are less and the potential applications of prod-
a recycling ratio (the amount of nonmetallic fractions in the phe- ucts are diverse (Ghosh et al., 2015).
nolic molding compound) of 20% was most reasonable. 15–30% PCBs high value glass-fibers can be separated from resins by flu-
nonmetallic fractions can be used as fillers for epoxy resins to pro- idized bed process technology with two stage cyclone separators at
duce composite boards. Composite boards are used extensively in 400–600 °C temperature and 1.0 m/s air velocity for 30 min. At
automobiles, furniture, amusement equipment and decorative 400 °C temperature, highest glass fiber recovery rate was 94.8%
materials. 30% nonmetallic fraction addition into thermoplastic and purity was 95.4% (Duan et al., 2011). Heat treatment after
Fig. 17. Motherboards, plastic CPU and ceramic CPU recycling plant flowsheet.
600 °C can damage and remove any surface treatment of glass sources of heavy metals without effective collection, reuse and
fiber. This process can produce a clean flue gas without violating recycling systems, they will be dangerous to environment. Recy-
environmental regulations. The glass fiber and resins contained cling of WEEE and reuse of some electrical/electronic parts are a
in nonmetallic fractions can enhance viscoelastic materials beneficial alternative than disposal. Waste PCBs account for about
(amorphous polymers, semi crystalline polymers, asphalt materi- 3–5% of nearly 50 million t/year global E-waste generations.
als) by composition effect. For several years, waste PCBs have been poorly managed by
informal recycling sector. The valuable metal components have
7.1. Perspective of alternative use of nonmetallic fraction been recovered using environmentally-unfriendly strong inorganic
acid leaching processes or pyrolysis which emits eco-unfriendly
In terms of the research into the utilization of the 70% non- gaseous pollutants (Chi et al., 2011). The 70% by weight nonmetal-
metallic fraction of PCB waste, the potential opportunities to lic fraction has been traditionally discarded to landfill or used as
generate and recycle value added products has not made the same very low cost fillers in the construction industry.
progress and is limited to: (Hadi et al., 2015). A significant amount of Cu and Au in e-waste attracts crude/
illegal recyclers in some parts of Asia and Africa leading to substan-
Incorporating the nonmetallic fraction into plastic molds has a tial environmental and health problems. Due to the heterogeneous
higher value than when it is used as a filler in cement and composition and hazardous material contents, proper recycling
asphalt industries. methodology is a still a challenging task. PCBs assay far above
The application in the production of adsorbent/resins for water many base and precious metals natural deposits and is therefore
treatment applications would represent a major breakthrough if recognized as a respectable poly-metallic secondary resource.
scale-up succeeds. The primary objective of recycling PCB scrap is to minimize the
Research into the production of silicon or the recovery of silica harmful environmental impact caused by hazardous material and
would also be attractive opportunities for new research on ensure maximum material recovery. To achieve these goals,
nonmetallic e-waste and provide sustainable recycling into detailed information of the PCBs and ECs are required for selecting
the microelectronics industry if successful. the right recycling method and facility (Li et al., 2004). The rapid
proliferation of electronic devices in the last few decades has
8. Concluding remarks compelled the researchers to find a remedy for one of the most
toxic and hazardous waste materials. Numerous articles have been
E-waste is one of the fastest growing municipal solid waste published demonstrating the process routes for recycling of this
streams worldwide today. WEEEs are one of the largest known toxic but otherwise useful waste due to nearly 30% metal content.
Dismantling of PCBs is the first and the most important step in treatment may lead to the formation of mixed halogenated dioxins
the recycling chain, which can help to conserve scarce resources, and furans (PXDD/Fs where X: Cl, Br). Waste PCBs can be used to
establish the reuse of valuable ECs and eliminate hazardous mate- produce a Cu-Ni-Si alloy, a mixed oxide (mainly Pb and Zn) and
rials from the environment. Some thermal process is almost inevi- slag by a top blown reactor.
table during the dismantling of PCBs. The removal of ECs from PCBs In contrast to physical separation, chemical separation gener-
includes a combination of heating to above the solder-melting ally involves decomposition of plastics through pyrolysis produc-
temperature and applying a shear force. The major common point ing oils, gases, tar, etc. Refining is the purification of recovered
of these disassembling technologies is the recovery of the solder materials by metallurgical processing so as they are acceptable
remaining on the board by subjecting it to a temperature for their original use. Purification and recovery of metals various
40–50 °C higher than the molten point of the solder, ranging methods and options are available for the purification and selective
200–280 °C (Duan et al., 2011). Pyrolysis probably occurs during recovery of the target metals from the pregnant leach liquor. These
thermal dismantling of PCBs. methods include solvent extraction, cementation, ion exchange,
The major hazards during e-waste recycling are associated with precipitation, adsorption, etc. The route to recover the metals
the size reduction and separation and hydro/pyrometallurgical depends upon the economy of the process and selectivity.
treatment steps. Shredding leads to the formation of fine dust com- However, very limited numbers of articles are available on purifi-
posed of plastics, metals, ceramic and silica. Additive chemicals cation and separation of individual metals from PCBs leach liquor
like BFRs which are embedded in WEEE are also released during (Ghosh et al., 2015).
shredding. Some of the base and valuable metals are lost during This present review indicates that while substantial research
comminution as well. needs to be done to pave the way forward for successful, environ-
Physical and hydro/pyrometallurgical methods have been the mentally friendly and economic waste PCB recycling, significant
traditional methods of recycling PCBs. Selective disassembly progress has been made both in the methods for separating PCB
targets and singles out hazardous and valuable components for waste into its metallic and nonmetallic fractions but also in
special treatment. Selective disassembly of hazardous components identifying more economically attractive uses for the 70% by
from the PCBs minimizes the toxic elements ending up in the weight nonmetallic component of e-waste. Potential applications
mainstream of the recycling process. Following the dismantling, of recovered nonmetallic fractions are diverse e.g. as filler material
good liberation of nonmetals from metals is required for effective or as composites having similar properties of traditional filler
separation. Upgrading increase the content of desired materials. materials. Recovered glass fibers perform better than commercial
In general, milling to size below 150 lm ensures no interlocking sound absorbing materials and have great potential as insulation
of metallic and nonmetallic particles. Many researchers have used materials. Nonmetallic fraction of waste PCBs have to be recycled
various mechanical methods (multi-stage crushing, pulverizing, environmental sound way. Combustion of these fractions in
electrostatic separation, gravity separation, density-based separa- municipal solid waste will cause the formation of highly toxic
tion and magnetic separation) to separates metals from nonmetals. PBDD/Fs and emissions of metal fumes while landfilling leaches
For physical separation the density-based separators are quite pop- out heavy metals to the groundwater and evaporates heavy metals.
ular. The latest developments include Corona electrostatic separa- The hazardous substances contained in nonmetal fractions are
tor, which is based on the difference in density and electrical mainly BFRs and heavy metals. Resin powder can be used in con-
conductivity between plastics, metals and ceramics with little struction materials and asphalts, if it can be physically recycled,
cross-contamination. Dry Corona electrostatic method is used at which is simple, cheap and environmentally sound. Physical recy-
room temperature and emits almost zero pollution depending on cling of the nonmetallic fraction is a promising recycling method
the quality of the dust extraction system. without environmental pollution and reasonable equipment
Hydrometallurgical route mostly focused on Cu recovery. investment and low energy cost (Guo et al., 2009). More work
Although sulfuric acid is the most preferable reagent for Cu leach- should be done to develop comprehensive and industrialized usage
ing but downstream processing becomes complicated due to poor of the nonmetallic fractions recycled by physical methods.
leaching selectivity in inorganic acids. Ammonia leaching, on the For long-term sustainability, an integrated efficient waste man-
other hand, has more selectivity towards Cu. Recycling of PCBs agement system primarily consisting of three key factors – reduce,
can only be profitable with substantial Au recovery. Thiosulfate reuse and recycle or better known as 3R policy (Terazono et al.,
and thiourea seem to be promising one alternative to cyanide for 2006), is the preferable approach. Reduction of waste at source is
Au leaching. An interesting approach for Au recovery is the persul- important. Considering the 3R policy, the highest emphasis should
fate based leaching where all base metals including Ag dissolve always be given on the recycle and reuse of the waste electronics
keeping Au in the solid residue, which can be later purified by to reduce the quantity of waste PCBs ending up in the disposal
melting. In the previous studies, 12–100% Cu, 6–62% Fe, 51–83% (Ghosh et al., 2015). Recycling with safe technology in an environ-
Zn, >90% Ni, 86–99.5% Au, 93% Ag and 99% Pd recoveries were mentally sound way, reduces the consumption of natural
achieved. resources, lowers the carbon footprint and lessens the environ-
Bioleaching has considerable potential to offer by selectively mental hazards. Extended producers’ responsibility for manufac-
extracting of the base and precious metals from PCB scraps at turing new EEEs should take into account lighter weight, longer
low temperatures by microorganism, such as bacteria and fungi, lasting, easier dismantled, nontoxic raw materials and lower cost
generated organic acids, thus significantly reducing the pollution products.
from strong acid leaching and also leaving an unpolluted non- E-waste is not a poison, waste or garbage. It is a valuable scrap.
metallic residue for further processing. Apart from low reaction E-waste should not be dumped illegally anywhere. Municipal
rate, metal precipitations as well as bacterial toxicity are some of dumps, children playgrounds, rivers, lakes, seas, etc. should not
the major issues projected by various researchers. be a graveyard for e-waste. There is a significant energy savings
For metal extraction, pyrometallurgy route has the main advan- from recycled materials. Recycled material energy savings over
tage of its ability to accept any forms of scrap but suffers from the virgin materials are 95% for Al, 85% for Cu, 74% for Fe and steel,
limitation of selective refining. Pyrometallurgical treatment 65% for Pb, 60% for Zn, 64% for paper and >80% for plastics
generates fumes of heavy metals (especially low melting points (Cui and Forssberg, 2003).
metals such as Hg, Pb, and Cd. Besides if the feedstock contained The author hopes that the coverage of above items in this paper
PVC or other plastics flame retarded with BFRs, pyrometallurgical will raise awareness of e-waste problem, e-waste management and
assist the scientific community, policy makers and other stake- Gramatyka, P., Nowosielski, R., Sakiewicz, P., 2007. Recycling of waste electrical and
electronic equipment. J. Achiev. Mater. Manuf. 20, 535–538.
holders to find the gap areas in achieving a cleaner, safer and eco-
Goosey, M., Kellner, R., 2003. Recycling technologies for the treatment of end of life
nomical recycling process. Traditional technologies may not meet printed circuit boards (PCBs). Circuit World 29, 33–37.
the future requirements of industry because of environmental con- Grabda, M., Kudkak, S.O., Rzyman, M., Shibata, E., Nakamura, T., 2009. Studies on
tamination, high cost and low efficiency. Evidently, more studies bromination and evaporation of zinc oxide during thermal treatment with
TBBPA. Environ. Sci. Technol. 43, 1205–1210.
are needed in the area of metal and nonmetal separation and Guo, F., 2007. Composite lead-free electronic solders. J. Mater. Sci. Mater. Electron.
recovery of valuable metals from PCB leach liquors. Author feels 18, 129–145.
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pulverized waste printed circuit boards. Environ. Sci. Technol. 42 (14), 5267–
recovery. But, developing any novel clean technology for recycling 5271.
valuable resources from PCBs will be of great importance. Guo, J., Guo, J., Xu, Z., 2009. Recycling of non-metallic fractions from waste printed
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effects of hazardous substances released from electrical and electronic Yoo, J.M., Jeong, J., Yoo, K., Lee, J.C., Kim, W., 2009. Enrichment of the metallic
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Zeng, X., Zheng, L., Xie, H., Lu, B., Xia, K., Chao, K., Li, W., Yang, J., Lin, S., Li, J., 2012. Muammer Kaya was born in Eskisehir-Turkey in 1960.
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electronic scrap. Resour. Conserv. Recycl. 21, 247–269. lurgical Eng. Dept. of McGill University in Canada in
Zhang, S., Forssberg, E., 1999. Intelligent liberation and classification of electronic 1985 and 1989, respectively. Prof. Kaya is interested in
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Zhang, X., Guan, J., Guo, Y., Yan, X., Yuan, H., Xu, J., Guo, J., Zhou, Y., Su, R., Guo, Z., mental Protection. He has been working as a full Prof. at
2015. Selective desoldering separation tin-lead alloy for dismantling of ESOGU since 1999. Prof. Kaya has worked as the director
electronic components from printed circuit boards. ACS Sustain. Chem. Eng. 3,
of ESOGU Research Center for 15 years and the also
1696–1700.
founder and first manager of ESOGU Vocational School
Zhou, Y., Qiu, K., 2010. A new technology for recycling materials from waste printed
circuit boards. J. Hazard. Mater. 175, 823–828. in Eskisehir-Turkey. Prof. Kaya is a member of TMS, CIM
and AIME.

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Waste Management 57 (2016) 64–90

Contents lists available at ScienceDirect

Recovery of metals and nonmetals from electronic waste by physical

E-mail address: [email protected]

3.1. Dismantling (manual, automated and semi automated) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 74

1. Introduction ments, government office machines (information technology (IT)

valuable resources together with plenty of heavy metals and

Fig. 3. Total e-waste generation of some countries in 2012 (https://www.statista.com/chart/2283/electronic-waste/).

Substances Occurrence in WEEE Possible adverse effects

recovery option. Open dumping is the most common form of

Fig. 5. Valuable elements found in e-waste (http://slideplayer.com/slide/4776306/).

Fig. 6. Export of e-waste in the world.

Board/substrate Single sided Double sided Multiple layered

Table 3 approximately one-fourth organic resin materials containing

Organic Material Ceramic Non-organic Material

Non spherical in shapes aer grinding Spherical in shapes aer grinding

Polymers (Plascs) Flame Retardants Glass-Fiber Ferrous Metals Nonferrous Metals

Mass Fracon 30% 30% 40%

Hazardous Precious Rear Earth Elements

Analysis: Loss on Ignion (VOC) (800oC)/Argon Diﬀerence Aqua regia leaching

* Ferro magnec ** Dia/Paramagnec

Fig. 9. 500 t/h capacity PCB recycling plant view.

Fig. 11. Hazardous and non-hazardous materials in e-waste (http://www.liquidtechnology.net/computer-e-waste-recycling-disposal/).

E-Waste E-Scrap WEEE

Remove reusable/ hazardous parts

1st Stage Size Reducon

Physical Separaon Processes

Gravity Separaon Process

Non Metals Plascs Metals

Recyclables Non Recyclables Flame Retardents Ferrous Non Ferrous

Magnec Separaon Process

Hazardous Precious Rear Earth Elements

Eddy Current /Corona Electrostac Separaon Process

Non Metals Non Ferrous Metals

Metallurgical Separaon Processes

Hydrometallurgy Pyrometallurgy Biohydrometallugy

alumina, alkaline and alkaline earth-oxides and small amounts of

3.5. Gravity separation

Gravity separation is based on the fact that every material par-

Fig. 14. Small scale PCB recycling plant layout.

Fig. 15. Pyrometallurgical recycling process of e-waste and Cu concentrate (https://www.emaze.com/@AOCLCZRT/Smelting-presentation-JD.pptx).

Lixiviant Cyanide Thiourea Thiosulfate Potassium persulfate Halide

M. Kaya / Waste Management 57 (2016) 64–90

M. Kaya / Waste Management 57 (2016) 64–90

Lixiviant HBF4 + H2O2 Ammonia-ammonium sulfate HNO3 HCl

Aspergillus niger, Penicillium simplicisimum

potassium persulfate and thiosulfate for precious metals leaching

65–95% Cu, Sn, Al, Ni, Pb, Zn

4Au þ 8ðK=NaÞCN þ O2 þ 2H2 O ! 4ðK=NaÞ½AuðCNÞ2  þ 4ðK=NaÞOH

In recent years, the recovery of Au by thiourea has gained

Au þ 2CSðNH2 Þ2 ! AuðCSðNH2 Þþ2 þ e ð3Þ

1–2 M H2SO4 along with Fe2(SO4)3, O2 and H2O2 as an oxidant/

3–12 h period. 6 M HNO3 at 80 °C for 6–24 h were also tested.

H2SO4 + H2O2 achieved better metallurgical performance than

with references. Previous studies, given in Table 7, achieved

Cu þ Fe2 ðSO4 Þ3 ! CuSO4 þ 2FeSO4 ð4Þ

81% Ni, 89% Cu, 79% Al, 83% Zn

Cu þ 1=2O2 ! CuSO4 þ H2 O ð6Þ

H2O2 is expensive; but, gives high Cu and Ag recoveries as com-

4Au þ 8ðK=NaÞCN þ O2 þ 2H2 O ! 4ðK=NaÞ½AuðCNÞ2 þ 4ðK=NaÞOH