Accepted Manuscript

A Review of Current Progress of Recycling Technologies for Metals from Waste

Electrical and Electronic Equipment

Lingen Zhang, Zhenming Xu

PII: S0959-6526(16)30245-1
DOI: 10.1016/j.jclepro.2016.04.004
Reference: JCLP 7009

To appear in: Journal of Cleaner Production

Received Date: 2 November 2015

Revised Date: 3 April 2016
Accepted Date: 4 April 2016

Please cite this article as: Zhang L, Xu Z, A Review of Current Progress of Recycling Technologies
for Metals from Waste Electrical and Electronic Equipment, Journal of Cleaner Production (2016), doi:
10.1016/j.jclepro.2016.04.004.

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Pyrometallurgical Electrochemical
Mild extracting Supercritical
Technology Technology
Environment-
High efficiency Integrated friendly High value-added
Recycling
WEEE Technologies
metals
Vacuum
Other Technologies metallurgical
Technology

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A Review of Current Progress of Recycling Technologies for

Metals from Waste Electrical and Electronic Equipment

Lingen Zhang and Zhenming Xu*

School of Environmental Science and Engineering, Shanghai Jiao Tong University, 800

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Dongchuan Road, Shanghai 200240, Peoples Republic of China

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Corresponding author: Zhenming Xu

E-mail: [email protected]

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Tel.: +86 21 54747495
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Fax: +86 21 54747495

School of Environmental Science and Engineering

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Shanghai Jiao Tong University

800 Dongchuan Road, Shanghai 200240, Peoples Republic of China

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Abstract

The development of the recycling technologies for waste electrical and electronic equipment

(WEEE) has entered a new stage. The WEEE disposing technologies have evolved from simple

disassembly, classification and sorting to high value-added utilization technologies. In the past

decade, some modified and novel technologies have been developed to recover metals from

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WEEE. This paper focuses on the recycling of metals from WEEE. The recycling principle,

separating process, and optimized operating parameters of existing technologies are summarized

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and discussed in detail. Based on traditional recycling technologies of WEEE, pyrometallurgical

technology and some mild extracting reagent, such as chloride medium, ammonia-ammonium and

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non-cyanide lixiviants can effectively recycle metals. Compared with the conventional acid and

cyanide leaching, they have vast improvements in aspect of environmental protection. More than

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98% of Cu and 70% of Au can be extracted. In addition, electrochemical technology, supercritical
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technology and vacuum metallurgical technology etc are also applied to recycle WEEE. The

recovery rate of Cu and Pb under optimum conditions are around 84.2% and 89.4% respectively in
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supercritical water oxidation (SCWO) combined with electrokinetic (EK) technology. Vacuum

technology has good environmental performance due to its avoiding discharge of waste water.
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Other new technologies such as ultrasound technology, mechanochemical technology, and molten
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salt oxidation technology have also been tried to recycle metals from WEEE. Regrettably,

although many endeavors to develop recycling technologies have been attempted, these
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technologies are still relatively single and limited because WEEE is a complex system. Hence, the

shortages and defects of each technology are discussed from the perspective of technological
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promotion and environmental protection. Furthermore, the outlook about the further development
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of recycling technologies for metals from WEEE is presented.

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Contents
Abstract ............................................................................................................................................. 2
1. Introduction ............................................................................................................................... 4
2. Selection and classification of research methods .................................................................... 10
3. Traditional methods to recycle metals from WEEE ................................................................ 11
4. Advanced technologies to recycle metals from WEEE........................................................... 12
4.1. Pyrometallurgical technology ......................................................................................... 12
4.2. Mild extracting technology ............................................................................................. 14

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4.3. Biometallurgical technology ........................................................................................... 18
4.4. Electrochemical technology ............................................................................................ 20
4.5. Supercritical technology.................................................................................................. 23

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4.6. Vacuum metallurgical technology ................................................................................... 25
4.7. Other novel technologies................................................................................................. 29

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5. Environmental and practical defects of advanced technologies .............................................. 31
6. Perspectives on recycling technologies ................................................................................... 35
6.1. Recycling technologies aspect ........................................................................................ 35
6.2. Environmental protection aspect ..................................................................................... 35

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7. Conclusions ............................................................................................................................. 36
Acknowledgments ........................................................................................................................... 39
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Appendix A. Supplementary data ................................................................................................... 39
Acronyms and Abbreviations .......................................................................................................... 39
References ....................................................................................................................................... 40
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Keywords: Recycling technology; waste electrical and electronic equipment (WEEE); metals;

environmental assessment.
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1. Introduction

With new technological innovation, the replacement of equipment is persistently accelerating

the occurrence of serious pollution problem resulting from waste electrical and electronic

equipment (WEEE). The global amount of WEEE produced and disposed is sharply increasing

over the past several decades. According to statistics of Kiddee et al (Kiddee et al., 2013), 500

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million tons of computers were discarded between 1997 and 2007 in the United States and 610

million tons of computers became obsolete in Japan by the end of 2010. The same statistics

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indicate more than 1.1 million tons/year WEEE are generated in China, particularly from

manufacturing industry, end-of-life appliances and imports from developed countries (Hadi et al.,

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2015a). Every year, 20-50 million tons of WEEE are generated worldwide and this figure is

growing by about 45 million tons/year (Ogunseitan, 2013).

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The waste electrical and electronic products are diverse, including printed circuit boards
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(PCBs), television sets, refrigerators, computers, cell phones, and batteries etc. Table 1 shows the

main components of typical WEEE, which were first listed in the Waste Electrical and Electronic
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Products Recycling Directory by Chinese government in 2011.

Table 1 Main components of typical WEEE (He and Xu, 2014)

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Typical WEEE Main components

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Refrigerator Tubes, liners, condenser, wires, refrigerant

Air conditioner Heat exchanger, motor, compressor, copper pipe, PCBs, wires, refrigerant
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Washer Tub, drain hose, motor, wires, salt waste

Television Deflection yoke, demagnetized coil, speaker, PCBs, wires, CRTs, LCD
Computer Speaker, battery, storage medium, PCBs, wires, CRTs, LCD
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Cell phones Plastic enclosure, battery, storage medium, PCBs, wires, LCD
Printer/duplicator Roller, toner, PCBs, wires, toner cartridge
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WEEE contains a variety of valuable materials, such as metals, glass, plastics and others. As

can be seen in Fig. 1, WEEE is mainly composed of metals (~60% weight), followed by plastics

(~15.21% weight), and CRT&LCD screen (11.87% weight).

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Fig. 1. Typical material fractions in WEEE (Wang and Xu, 2014)

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Although WEEE accounts for only 3-5% in solid waste, the varieties and contents of valuable

metals in it are far more than other forms of municipal waste (Li et al., 2015). As shown in Table

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2, WEEE such as printed circuit boards, TV scrap has high content of base metals and the
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electronic devices such as personal computers and mobile phone scrap contains a large number of

precious metals (Akcil et al., 2015; Cui and Zhang, 2008). Therefore, WEEE is worthy of the
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name of "urban mine ". According to a survey by Environmental Protection Agency, U.S.,

compared with primary metals production, recycling metal resources from WEEE has significant
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advantages, such as less secondary waste and lower energy consumption (He, 2006).
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Table 2 Weight composition and value distribution of metals for different WEEE (Cui and
Zhang, 2008)
Content and value distribution for different WEEE (%) (in brackets)
Electronic waste
Weight (%) Weight(g/t)

Fe Cu Al Pb Ni Ag Au Pd
28 10 10 1 0.3 280 20 10
TV board scrap
(4) (39) (13) (2) (5) (6) (25) (6)
7 20 5 1.5 1 1000 250 110
PC board scrap

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(0) (10) (1) (0) (1) (64) (5) (15)
5 13 1 0.3 0.1 1380 350 210
Mobile phone scrap
(0) (8) (0) (0) (0) (5) (67) (19)
62 5 2 0.3 0.05 115 15 4
DVD player scrap

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(17) (35) (4) (1) (1) (4) (33) (4)
4.5 14.3 2.8 2.2 1.1 639 566 124
PC mainboard scrap
(0) (6) (0) (0) (2) (2) (81) (8)

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12 10 7 1.2 0.85 280 110 -
Printed circuit boards scrap
(1) (19) (4) (1) (6) (3) (66) -
- 3.4 1.2 0.2 0.038 20 <10 <10
TV scrap (CRTs removed)
- (82) (9) (2) (4) (3) - -
4 3 5 0.1 0.5 260 50 5

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Calculator scrap
(1) (12) (6) (0) (8) (6) (64) (3)
23 21 1 0.14 0.03 150 10 4
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Portable audio scrap
(3) (78) (1) (0) (0) (3) (12) (2)
8 20 2 2 2 2000 1000 50
Typical electronic device scrap
(0) (5) (0) (0) (2) (3) (87) (2)
27.3 16.4 11 1.4 - 210 150 20
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E-scrap sample
(1) (22) (5) (1) - (2) (65) (4)

However, WEEE contains not only all kinds of metals, but other chemical components which
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are also quite complicated, such as plastics and brominated flame retardants (BFRs). If WEEE is
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not disposed or recovered properly, it will cause serious environmental pollution and even

jeopardize human health (Wang and Xu, 2015). The main hazardous and useful materials of
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typical WEEE components are shown in Table 3. It has been reported that the occurrence of

recycling of WEEE by environment-unfriendly, hazardous and primitive technologies in China has

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increased in the past decades (Ni et al., 2010). Massive amounts of dumping or open burning of
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WEEE took place in some cities of China.

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Table 3 Main hazardous and useful materials in components of typical WEEE (He and Xu,
2014)

Component Hazardous materials Useful materials

PCBs heavy metals, brominated flame retardants glass fibre, resin, copper
Refrigerator cabinet Freon copper, aluminium, plastic
Toner cartridge toner aluminium, steel, plastic aluminium, steel, plastic
CRT Pb (PbO) glass

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LCD panel liquid crystal, TAC, PVA glass, In2O3
Wire polychlorinated biphenyls copper, aluminium, plastic
Li-ion battery LiPF6 steel, Al, Cu, Li, Co

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Ni-Cd battery Cd steel, Fe, Ni

Therefore, research on resource reutilization and safe disposal of the metals from WEEE has

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a great significance from the viewpoint of environmental protection. In the initial stage of WEEE

recycling, simple and rough recovery processes were widely adopted. As shown in Fig. 2, ways of

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recycling metals from WEEE mainly include manual dismantling, hydraulic shaking bed
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separation and strong acid leaching etc. The defects of these methods are huge, as they not only

have low recovery efficiency, but also damage human health and environment. Facing the serious
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issue resulting from crude recycling of WEEE, the European Union Council passed WEEE

Directive and the Restriction of Hazardous Substances (RoHS) Directive to limit the harmful
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composition in electronic products in January 2003. In the last decade, China has followed the
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same legislative trends and developed WEEE laws and directives (Gottberg et al., 2006).
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Fig. 2. (a) Manual dismantling and (b) hydraulic shaking bed separation to recycle metals in
WEEE
Entering the 1970s, mechanical-physical separation methods began to be utilized to treat the

WEEE (Zhang and Forssberg, 1998). Mechanical-physical separation steps included selectively

dismantling, crushing and physical separation methods. The separating situations for the physical

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separation technologies are summarized Table 4.

Table 4 A summary of separating situation for the physical separation technologies (Ruan
and Xu, 2016)

Physical separation
Character of separation Main advantages and disadvantages
method

MS was most suitable separating steel or iron but not

Magnetic separation (MS) separation of ferrous metals
suit separating of nonferrous metals

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ECS was encouraged to recover nonferrous metallic
Eddy current separation Separation of ferrous and
particles and hard to separate ferrous metals/other
(ECS) nonferrous materials
metals

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Air current separation separation of light particles wind velocity, particle size, particle density etc was
(ACS) from heavy particles the critical influences for ACS

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separate metallic particles the movement trajectory and collection position of
Corona electrostatic
(size from 0.2 mm to 1 mm) metallic particles in CES were hard to predict and
separation (CES)
from nonmetallic particles compute

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The methods of magnetic separation and eddy current separation are usually chosen to
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separate ferrous and nonferrous metal particles. Mechanical-physical separation technologies have

achieved good effects in aspect of practice and environmental protection. They have been adopted
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by most of the recycling enterprises in China. An integrated mechanical-physical recycling

technology for WEEE was established by Xu and his team (Li et al., 2007; Li and Xu, 2010),
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including two-step crushing, corona electrostatic separation, to recover metallic and nonmetallic
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materials (Huang et al., 2009a). Eddy current and electrostatic separation methods have achieved

recovery for magnetic metals, such as Fe, Ni, Co etc (Habib et al., 2013; Jujun et al., 2014; Menad
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et al., 2013). Furthermore, non-metal materials from WEEE also achieved recycling as padding

(Guo et al., 2010a, b). Fig. 3 shows an automatic production line of corona electrostatic separation
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and eddy separation equipment.

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Fig. 3. (a) An automatic production line of corona electrostatic separation and (b) eddy

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separation equipment
Regrettably, mechanical-physical recycling technology for the most of single metal from

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WEEE cannot achieve effective recycling. Now, one of the biggest challenges in terms of the

recycling technologies for WEEE is how to further classify and recycle high value-added metals

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from WEEE through scientific and effective ways/methods.
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As a matter of fact, WEEE is a complex system, containing various organic substances, and

metals. Therefore, the methods and technologies of recycling metals from WEEE are totally
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different from technologies of mineral separation. In order to develop and implement both

environmentally friendly and economically viable recycling processes of metals, a large number of
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novel technologies are proposed in recent years and mainly include: pyrometallurgical technology,
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mild extracting technology, electrochemical technology and vacuum metallurgical technology etc

(Rocchetti et al., 2013; Weeden et al., 2015).

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Pyrometallurgy has been successfully realized industrialization. Its principle involves metals

enrichment by smelting and converting, refining and other processes to remove the non-metallic
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material from WEEE. In this process, the crushed scraps are burned in a furnace or in a molten
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bath to remove plastics. The refractory oxides form a slag phase together with some metal oxides

(Cui and Zhang, 2008; Flandinet et al., 2012). Traditional hydrometallurgical process is associated

with acid or alkaline solutions to solubilize crushed WEEE. This process is called leaching. But in

recent decade, hydrometallurgical technology has begun to pay more attention to

environment-friendly recycling metals. Some mild leaching agents and modified technologies are

proposed, which offer more exact, relatively low construction costs and a certain recovery rate of

metals with their suitability for small scale applications. In recent years, extensive studies and

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practices have been carried out on recycling metals from WEEE by vacuum metallurgical

technology which separates and recycles materials through several kinds of means like vacuum

evaporation, vacuum sublimation (Zhan and Xu, 2009, 2011, 2012), vacuum reduction (He et al.,

2014), vacuum pyrolysis (Zhou and Qiu, 2010; Zhou et al., 2011), etc. Vacuum metallurgical

technology has some advantages on the separation of metals, such as low energy consumption and

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significant economic benefits.

Although special advantages come from these technologies, defects accompany also. These

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recycling processes for metals are relatively single, limited, and some methods still have negative

effects on environment. Therefore, it is necessary to summarize and discuss in detail the current

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status of recovery technologies for base and precious metals from WEEE. This paper focuses on

the recycling of metals from WEEE, reviews features and defects of the existing technologies.

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Based on environmental protection and resource recycling utilization for the metals, some novel
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and environment-friendly ideas are proposed in this article. Meanwhile, the outlook on the further

development of recycling technology is presented for the metals from WEEE.

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2. Selection and classification of research methods

Selection and classification of research methods were divided into three steps:
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(1) Selection and classification of literature: the first step of this research is to conduct literature
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reviews by a comprehensive search on the Scopus, Elsevier and Web of Science database,

using as key words WEEE AND metals AND recycle AND technology AND
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metallurgical and so forth. The abstracts of the most relevant papers according to their title

were assessed to examine whether they fall under the scope of the study. In addition, already
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published reviews on recycling areas of e-waste were identified and utilized to get available
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methods and technologies. The literatures were classified according to different recycling

technologies, metals type (base metals and precious metals) and the means of pollution

control.

(2) Selection and classification of recycling technologies: for traditional recycling technologies,

such as pyrometallurgical and hydrometallurgical technology, we chose the technologies

which had prominent improvement in the aspects of environmental protection. In addition,

some new/novel technologies in recent decades were also focused. These technologies had

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great significance for recycling metals in the view of pollution control and recovery efficiency.

They included biometallurgical technology, electrochemical technology, supercritical

technology, and vacuum metallurgical technology etc.

(3) Evaluation of technological processes: these methods/technologies were classified into seven

specific categories to facilitate their analysis and evaluation. We focus on each category of

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method/technology to further search in databases. A filtered work of literatures for a certain

technical process was carried out. And then, according to the ideas, devices and results of

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experiments in literatures, we selected representative examples from each recycling

technology to summarize and review. Finally, some shortages and improvements of these

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recycling processes were proposed from relevant research papers, review papers and some

production processes. Hence, this paper reviewed representative and innovative technologies

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to clarify current progress of recycling metals in WEEE.
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3. Traditional methods to recycle metals from WEEE

Traditional methods of recycling WEEE are incineration, hydraulic shaking bed separation
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and acid leaching process. For incineration process, WEEE is directly burned in the blast furnace.

The product in the blast furnace contains 70-85 wt. % black copper. This black copper is fed into
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the converter to be oxidized and then is reduced in the anode furnace. The recovered anode copper
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can be further purified in H2SO4 electrolyte with other elements, such as Ni, Zn, and Fe (Kang and

Schoenung, 2005). The hydraulic shaking bed separation was widely used for recycling metals in
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waste PCBs in the past. Crude copper particles can be obtained by this process. However, this

process generates huge amounts of wastewater and residues (Huang et al., 2009a). If not handled
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properly, waste water and residues can cause serious secondary pollution. In addition, it is hard to
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recover other metals except copper, and nonmetal materials cannot be recycled.

Traditional hydrometallurgy processes are acid leaching to recover metals (Watling, 2013).

HNO3/HCl/HClO4 is used as leaching solvent to extract metals such as Cu, Pb, and Zn etc from

WEEE. In the past, nitric acid was also used in combination with hydrochloric acid in the form of

aqua regia for non-selective and aggressive digestion of base and precious metals (Cu, Pb, Zn, Ag

etc.) from WEEE (Bas et al., 2014; Castro and Martins, 2009; Sheng and Etsell, 2007). Cyanide

leaching precious metal Au has been used for more than one century due to the selectivity and

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stability of dicyanoaurate complex (Kulandaisamy et al., 2003; Quinet et al., 2005). The cyanide

as leaching agent has a major issue, its toxicity, that may cause environmental and workers safety

problems if used improperly. These traditional methods are not only inefficient but also greatly

damaging to the environment. In recent years, on the basis of traditional technologies, some

advanced recycling technologies are put forward and have gained considerable progress.

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4. Advanced technologies to recycle metals from WEEE

4.1. Pyrometallurgical technology

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Pyrometallurgical technology has been significantly improved in terms of the recycling

technologies and the treatment of pollutant. Pyrometallurgy can successfully realize

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industrialization, including a series of steps, such as dismantling, smelting in a plasma arc furnace,

drossing, sintering, melting and reactions in a gas phase at high temperatures. In this process, the

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crushed scraps containing metals (including base and precious metals) are burned in a high
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temperature furnace, and then the metals are volatilized by a chemical reaction or by heat, and

impurities are converted into slags.

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Generally, WEEE needs to be treated firstly through the mechanical-physical pretreatment:

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dismantling main parts; shredding/grinding processes for size reduction and liberation of

components etc. And then, enriched metals are smelted in furnaces and coarse metal ingot can be
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obtained. In most cases, smelting process is most important process for pyrometallurgy. The two

basic and widely applied smelting processes include flash smelting and bath smelting. Flash
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smelting employs oxygenated gas to promote autogenous conditions while bath smelting depends

on the roasting and smelting steps, and reaction occurs in a molten pool containing both melts and
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slag phases (Montenegro et al., 2013). Some advanced smelting equipments have been used in
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pyrometallurgy, such as Outokumpu flash smelting, Noranda reactor system and Mitsubishi

continuous smelting (Kucharski et al., 2014; Moskalyk and Alfantazi, 2003). The next step is

converting process. In the copper converters, matte can be obtained from the converting unit by

blowing in air from tuyeres. This step can oxidize the iron sulphide and convert copper sulphide to

metallic copper. The last procedure is refining units with the purpose to get high purity copper in

the reverberatory or rotary furnaces (Hagelken, 2006). The pyrometallurgical process of

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recycling copper in WEEE is shown in Fig. 4.

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Fig. 4. A schematic flow sheet showing recycling copper in WEEE by pyrometallurgy processes

An application for pyrometallurgical process to recover metals from WEEE was practiced at
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the Boliden Ltd. Rnnskr Smelter, Sweden. The schematic diagram for the Rnnskr Smelter is

shown in Fig. 5a. More than 100,000 tonnes of e-scraps including WEEE were fed into Kaldo
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Furnace every year (Cui and Zhang, 2008). The e-scraps can be fed into the process in different
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steps according to their purities. Some e-scraps containing high content of copper were fed into

converting process directly, but low grade e-scraps were fed into Kaldo Furnace. And further the
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mixed copper alloys produced in Kaldo Furnace were sent to the converting process to recover

metals (Cu, Ag, Au, Pd, Ni, Se, and Zn). The dusts containing Pb, Sb, In and Cd were sent to other
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operations to further recover (Cui and Zhang, 2008; Ek and Olsson, 2005; Isaksson and Lehner,
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2000).

Another application for pyrometallurgical process was the plant of Umicore integrated

smelter and refinery. This process mainly focused on recovery of precious metals from WEEE

including Ag, Au, Pt, Pd, Rh, Ru and Ir. The schematic diagram for the Umicore Smelter is shown

in Fig. 5b. Its procedures included: firstly, WEEE was pretreated (i.e. dismantling, shredding and

physical processing) and then the precious metals operations (PMO) were smelted in an Isa Smelt

furnace. Almost all other metals were concentrated in the slag after smelting; thirdly, the slag was

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further treated at the base metals operations (BMO). The base metals were the byproducts from the

PMO which were subjected to electrolytic refining to gain high purity base metals, such as copper

(Le Ret and Briel, 2011; Tuncuk et al., 2012).

A crushing-pyrometallurgical process of waste fluorescent lamps was applied by Nomura

Kohsan in Japan (the flow sheet as shown in Fig. 5c). This process concentrated on the extraction

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of base metals, rare earth metals and mercury in the recycling of fluorescent lamps. The waste

fluorescent lamps were calcinated in vertical calcinatory and then underwent refining process to

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get rare earth metals and mercury (Yufeng et al., 2014).

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Fig. 5. Schematic diagram for (a) Rnnskr Smelter; (b) plant of Umicore and (c) recycling
process of fluorescent lamps (Cui and Zhang, 2008; Tuncuk et al., 2012; Yufeng et al., 2014)

4.2. Mild extracting technology

Modified and new hydrometallurgical technologies have becoming a hot spot of recent

researches. They are more targeted towards metals recovery or pretreatment, easier to control

chemical reaction, and make relatively less pollution than pyrometallurgical technology (Ghosh et

al., 2015a). Some mild leaching agent for hydrometallurgy were proposed, such as leaching

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process of chlorinate (He and Xu, 2015), ammonia-ammonium (Koyama et al., 2006; Sun et al.,

2015; Xiao et al., 2013) and non-cyanide lixiviants for leaching Au (Akcil et al., 2015) etc.

Several chloride-based leaching processes were developed and presented at the lab/pilot scale.

A chloride medium (HCl-CuCl2-NaCl) to extract copper were utilized. Cupric ion (Cu2+) acting as

an oxidant can form stabilization of cuprous (Cu+) when a suitable ligand such as chloride ion (Cl)

was added to sulphate solution (Yazici and Deveci, 2015). Cu2+ also might present as

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chloro-complexes ( CuCl 2n n ) in chloride solutions (Yazici and Deveci, 2013). The equations of

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reaction are described:

Cu 0 + Cu 2+
2Cu +

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Cu + + nCl
CuCln1n
Cu 0 + Cu 2+ + 2Cl
2CuCl ( s) (G298 K = 41kJ / mol ) (1)
2+

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Cu + Cu + 4Cl
0
2CuCl AN2 (G298 K = 25kJ / mol )

The results showed that increasing the initial concentration of Cu2+ to 79 mmol/l can improve the

extraction of metals with almost complete extractions (98%) for Cu at a leaching period of more
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than 120 min. Yazici et al. (Yazici and Deveci, 2013, 2015) used H2SO4-CuSO4-NaCl leaching

system to extract the metals from waste PCBs. The effect of initial concentration of cupric (0.5-7.5
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g/L Cu2+), chloride (4.7-46.6 g/L Cl) and temperature (20-80 C) on the leaching of copper was
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investigated. The results demonstrated that the extraction of metals had significantly improved

with increasing temperature and Cu2+ concentration. The Cl/Cu2+ molar ratio was importance for
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the extraction process, because Cl and Cu2+ had a strong interaction in leaching process.

The method of ammonia-ammonium leaching has superiority in terms of selectivity towards

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copper (Liu et al., 2009). An ammonia-ammonium sulfate and chloride systems were used to
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recover Cu from waste PCBs. Ammonia-ammonium salt solution containing Cu(I) and Cu(II)

ammine complexes were used as the leaching agent. The process consisted of two stages: leaching

and purification. In the stage of leaching, Cu in the waste PCBs was oxidized by Cu(II) to form

Cu(I)-ammine complex ions, resulting from the decreased oxidation-reduction potential during the

leaching. The leaching reaction can be expressed as:

2+ +
Cu + Cu(NH3 ) 4 2Cu(NH3 ) 2 (2)

The Cu(II)-ammine complex significantly enhanced the leaching rate of Cu (leaching rate > 95%).

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In the stage of purification, an electro-winning technology had been proposed to recycle Cu in the

Cu(I)-ammine complex (Cu(NH3)2+) (Koyama et al., 2006; Oishi et al., 2007). They focused on

the leaching mechanism and behavior of copper by electro-winning. Lim et al. (Lim, 2013) tried to

use NH3/NH4Cl with oxidants CuCl2 leaching to recover metals Cu from alloy obtained from

smelting reduction process of mobile phone PCBs. It was observed that 98% Cu can be leached

under the following conditions: 2 kmol/m3 NH4Cl and 5 kmol/m3 NH3 solution, 0.1 kmol/m3

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CuCl2 at 30 oC.

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In order to overcome the disadvantages of cyanide leaching precious metals, considerable

efforts have been made to research for non-cyanide systems. Hence, several non-cyanide lixiviants

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have been proposed and are regarded as being the most realistic substitutes in recent years, such as

thiourea (Li et al., 2012a), thiosulfate (Chandra and Jeffrey, 2005; Ha et al., 2010; Jeffrey and

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Brunt, 2007).
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Thiourea ((NH2)2CS) used as a gold extracting agent for WEEE has shown significant

advantage due to its high rate of leaching, lower toxicity and eco-efficiency (Gurung et al., 2013;
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Ubaldini et al., 1998; Vinh Hung et al., 2010; Wronski and Luczak, 2010). The content of leaching

of gold is contingent upon careful optimization and control of pH, redox potential, thiourea
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concentration, and leaching time. The reaction follows the equation:

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+
Au + 2SC( NH 2 ) 2 Au (SC[ NH 2 ]2 ) 2 + e (3)

In addition, the combination of lixiviants can produce a synergistic effect. The effect was
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evident using ferric sulfate as the oxidant for leaching Au (Broadhurst and Dupreez, 1993; Li and

Miller, 2007). The gold leaching reaction in acid thiourea-ferric sulfate solution can be represented
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by the following reaction:

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+
Au + 2SC ( NH 2 ) 2 + Fe 3 + Au (SC[ NH 2 ]2 ) 2 + Fe 2 + ( 4)
The conclusion showed that the ferric ion presented in acidic thiourea solutions can significantly

affect the reaction kinetics of gold cementation. The leaching rate of gold depended on ferric

concentration; ferric ion increased significantly the redox potential of the solutions, but the

leaching rate kept constant with time when thiourea concentration was below 12 g/L and ferric

was above 0.1 g/L (Birloaga et al., 2013). Birloaga et al. (Birloaga et al., 2014) utilized two

chemical leaching systems to recycle the base and precious metals from waste PCBs, that is, the

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first step was the leaching system of sulfuric acid with hydrogen peroxide, meantime thiourea with

the ferric ion in sulfuric acid medium was used as the second step. The results indicated that 2

mol/l H2SO4 (98% w/v), 5% H2O2, 25 oC, 1/10 S/L ratio and 200 rpm were founded as optimal

conditions for Cu extraction and extraction rate of Cu can reach approximately 100%. For thiourea

acid leaching process, 20 g/L of CS(NH2)2, 6 g/L of Fe3+, 0.5 M H2SO4 were founded as optimal

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conditions for Au extraction and extraction rate of Au exceeded 70%.

On the basis of leaching Au by acidic thiourea in the presence of ferric iron, a modified

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hydrometallurgical technology was proposed for selective recovery of Cu, Ag, Au and Pd from

waste PCBs. Firstly, through two consecutive sulfuric acid leaching steps in the presence of H2O2

SC
as oxidizing agents, more than 99% of copper was dissolved. The 2nd leaching step was acidic

thiourea in the presence of ferric iron as oxidizing agent to leach the solid residue, which 85.76%

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Au and 71.36% Ag was achieved. The leaching of Pd and remained Au from the solid reside of
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3rd leaching step was performed in NaClO-HCl-H2O2 leaching system, and then palladium and

gold were precipitated by sodium borohydride. 100% of Pd and Au of what was in the chloride
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leachate were precipitated by using 2 g/L sodium borohydride (Behnamfard et al., 2013).

Thiocyanate is also an effective lixiviant for gold in acidic conditions. The thiocyanate
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system has been considered to effectively dissolve and recycle gold and silver from gold-bearing
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WEEE. One important characteristic of the thiocyanate ion is that it can form stable and soluble

complexes of aurothiocyanate (Au(SCN)2), and aurithiocyanate (Au(SCN)4) (Li et al., 2012b).

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The equation of reactions is as follows:

2SCN - + Au = Au( SCN ) 2 + e (5)
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4SCN + Au = Au( SCN ) 4 + e
-
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In sulfuric acid solutions with ferric as oxidizing agent, thiocyanate presents and gold dissolves

according to reaction:

Au + 2SCN - + Fe 3 + = Au ( SCN ) 2 + Fe 2 + (6)

The mechanism of dissolution of gold by ferric-thiocyanate solution was considered as an

auto-reduction process, namely, ferric was spontaneously reduced to ferrous while oxidizing SCN.

This oxidation was considered through forming several intermediate species, in particular (SCN)3

and (SCN)2, which acted both as oxidants and as complex for gold (Li et al., 2012c, d, e).

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Follow by above studies, the leaching of gold has been studied by the combining method of

thiourea-thiocyanate, using ferric sulfate as oxidant (Yang et al., 2011). The gold leaching was

higher than either ferric-thiocyanate or ferric-thiourea solutions respectively. The explanation was

that the synergistic effect was attributed to the formation of a mixed ligand complex

Au(SC[NH2]2)2SCN.

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Recently, some organic acids are introduced as environment-friendly leaching reagents. For

example, citric acid and hydrogen peroxide, DL-malic acid or other extraction agents as leaching

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reagents were introduced to leach cobalt and lithium from lithium-ion batteries (LIBs) (Jha et al.,

2013; Li et al., 2010a; Li et al., 2010b). Extraction agent as PC-88A, D2EHPA, and Cyanex 272

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were used to separate and purify the metals (Chen et al., 2011; Dorella and Mansur, 2007; Swain

et al., 2006; Swain et al., 2007; Xu et al., 2008). Separation of base and precious metals from

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WEEE using environment-friendly, low corrosive leaching reagents, such as NH3H2O/KI for Pd,
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Pt (Dawson and Kelsall, 2007), and (NH4)2S2O3/CuSO4/NH4OH/O3-Cl- for Ag, Au was also

widely investigated (Oh et al., 2003; Vinals et al., 2006; Vinh Hung et al., 2014; Zhang and Zhang,
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2013). Supporting Information Table S1 summarizes main processes and reactions of modified

hydrometallurgical technologies to recycle precious metals Au.

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4.3. Biometallurgical technology

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Biometallurgical process is well used in mineral processing as an alternative technology for

recovering metals from very low-grade ores and concentrates (Watling, 2006). However, most of
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applications of the biometallurgy for recovering WEEE are still in a laboratory scale. There are

two main field of biometallurgy for recovery of metals, namely bioleaching and biosorption.
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Bioleaching is technically feasible by the use of bacteria-assisted reaction to extract base

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metals such as Cu, Ni, Zn, Cr and precious metals from WEEE such as Au, Ag in current results of

laboratory scale. For bioleaching, acidophilic group of bacteria plays an important role in

bioleaching of heavy metals such as Acidithiobacillus ferrooxidans, Acidithiobacillus thiooxidans,

Leptospirillum ferrooxidans, and Sulfolobus sp (Debaraj, 2010; Liang et al., 2010; Panda et al.,

2015). For example, Wang et al. (Wang et al., 2009) used bioleaching processes to mobilize metals

from waste PCBs. The bacteria Acidithiobacillus ferrooxidans (A. ferrooxidans) and

Acidithiobacillus thiooxidans (A. thiooxidans) were grown and acclimated in waste PCBs and

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then used as bioleaching bacteria to solubilize metals. The results demonstrated that all the

percentages of Cu, Pb, and Zn solubilized into the leaching solution from PCBs. The concentration

of PCBs should be controlled under the range from 7.8 to 19.5 g/l. Under 7.8 g/l of the

concentration of PCBs, the dissolution rate of Cu are 99.0%, 74.9%, 99.9% at 0.5-1.0 mm of sieve

fraction at 9d of leaching time by the pure culture of A. ferrooxidans, the pure culture of A.

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thiooxidans, and mixed culture of A. ferrooxidans and A. thiooxidans, respectively. Similar studies

also showed the leaching content of Cu increased when the amount of the ferrous ion increased in

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the solution up to 7 g/L with Acidithiobacillus ferrooxidans (Yang et al., 2009; Yang et al., 2014).

Karwowska et al. (Karwowska et al., 2014) evaluated the possibility of bioleaching Zn, Cu, Pb, Ni,

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Cd and Cr from waste PCBs by using a culture of sulphur-oxidising bacteria and a mixed culture

of biosurfactant-producing bacteria and sulphur-oxidising bacteria. The results showed that 48%

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Zn and 93% Cd was dissolved in both media. For Ni and Cu, a better effect was obtained in the
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acidic medium with a removal rate of 48.5% and 53% respectively. Pb was removed with very low

effectiveness (below 0.5%).

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Biosorption process is a physico-chemical and metabolism-independent process resulting in

the removal of substances from solution by biological materials (Gadd, 2009). The properties of
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certain types of inactive or dead microbial biomass materials also allow them to bind and
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concentrate metal ions from industrial effluents and aqueous solutions. Biosorbents are prepared

from different microorganisms including bacteria, fungi, algae, actinomycetes, yeasts and some
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biowaste materials on precious metal biosorption. Au(III) was successfully recovered as metallic

gold nanoparticles using dead biomass of the brown alga F. vesiculosus by the study of Mata et al.
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(Mata et al., 2009) The results indicated that the brown alga F. vesiculosus can recover and reduce
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Au(III) to Au(0). The greatest gold uptakes were obtained at initial pH values between 4 and 9,

with an optimum at pH 7. The marine alga Sargassum natans and the fungal cells of Aspergillus

niger, Mucor rouxii and Rhizopus arrihus were also found to take up precious metals like gold

(Das, 2010). Tasdelen et al. (Tasdelen et al., 2009) investigated recovery of gold from synthetically

prepared diluted gold-bearing solutions of 50 ppm using DEAE-cellulose, a common biopolymer

derivative. The results demonstrated that gold can be effectively recovered using excessive

amounts of DEAE-cellulose (at DEAE-cellulose/Au weight ratios of 400 and above) and recovery

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rate of gold was found to be over 99%. Table 5 lists some recycled efficiency of base and precious

metals by bioleaching and biosorption.

Table 5 Recovery of base and precious metals by bioleaching and biosorption (Das, 2010;
Ghosh et al., 2015b)

Microorganisms Recovery Rate (%)

Thiobacillus thiooxidans + T.
ferrooxidans Cu, Ni, Al, Zn >90%

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Aspergillus niger Cu, Sn 65%
Penicillium simplicissimum Al, Ni, Pb, Zn >95%
Acidithiobacillus ferrooxidans Cu 81.6%
Acidiphilium acidophilum (ATCC Cu 3.6%, Ni 86% Zn

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27807) 40.8%
Bioleaching Sulfobacillus thermosulfidooxidans + Ni 81%, Cu 89%, Al
acidophilic heterotroph (AlTSB) 79%, Zn 83%
Chromobacterium violaceum Au 68.5%

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A. ferrooxidans Cu 99%
A. ferrooxidans Cu 99%
A. ferrooxidans + A. thiooxidansgenera Cu 96.8%, Al 88.2%, Zn
Acidithiobacillus and Gallionella 91.6%

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Thermosulfidooxidans sulfobacilllus +
Cu 95%
Thermoplasma acidophilum
Acidithiobacillus Thiooxidans Cu 98%
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Max of adsorption
Adsorbents
quantity (mmol/g)
Algae
Fucus vesiculosus Au, 0.35
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Dealginated Seaweed Waste Au, 0.4

Chlorella vulgaris Au, 0.5
Sargassum natanss Au, 2.1
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Chlorella vulgaris Au, 0.5

Fungi
C. cladosporioides strain 1 Au, 0.4
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C. cladosporioides strain 2 Au, 0.5

Fomitopsis carnea Au, 0.48
Biosorption
Cladosporium cladosporioides Au, 0.5
Aspergillus niger Au, 1
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Rhizopus arrhizus Au, 0.8

Bacteria
Streptomyces erythraeus Au, 0.03
Desulfovibrio desulfuricans Pd 1.2, Pt 0.32
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Desulfovibrio fructosivorans Pd 1.0, Pt 0.17

Others
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Chemically modified chitosan Au 3.4

Bisthiourea derivative of resins Au 3.63
Thiourea derivative of chitosan Pt 2.0
Chitosan derivatives Pt 3.2, Pd 3.5

4.4. Electrochemical technology

Electrochemical process is promising technology and offers unique method to recover base

and precious metals from WEEE due to high environmental compatibility, high energy efficiency

and minimal chemical usage. Some researchers reported this technology to recover metals from

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WEEE.

Kim and his colleagues (Kim et al., 2011b) developed a process of electro-generated chlorine

to carry out the leaching of metals from waste PCBs. The technology of electro-generated chlorine

has the advantage of leaching precious metals because of acquiring high oxidation potential (Kim

et al., 2011b). Fig. 6a shows the schematic diagram of separate reactors consisted of an

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electrolytic cell for chlorine generation. Two cathodes and anodes were used and hydrochloric acid

was poured into the leaching reactor. Anode reaction can be represented by the following equation:

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2Cl - = Cl 2 (electrode surface) + 2e - (7)

And the dissolution of gold reaction as:

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Au + Cl- + 3 / 2Cl2 (aq) = AuCl4 (aq) G298K = 27.04kcal / mol (8)

Au + 3 / 2HClO+ 3 / 2H + + 5 / 2Cl = AuCl4 + 3 / 2H2O G298K = 33.29kcal/ mol

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They found that the content of leaching of gold was increased with increasing of temperature and

initial concentration of chlorine, and was favorable even at low concentration of acid. But the
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leaching of copper was different, that is, leaching increased with increasing of concentration of

acid and decreasing of temperature. In total leaching process, 97% copper was dissolved and the
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recovery rate of gold was 93% in the separate reactor. A combined reactor (Fig. 6b) with
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simultaneous Cl2 generation and metal leaching which can circulate and reuse chloride ion without

additional supplementation, was compared with the separate reactor for the recovery effect of
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metals (Kim et al., 2011a). It was observed that the leaching rate of Cu increased with increase in

current density, temperature and time in both reactors. The dissolution of Cu was about 20% and
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25% in the combined and separate reactor respectively with the copper leaching rate gradually
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diminished. This result may be attributed to the surface area of copper forming CuCl(s) with

increasing of leaching time. And the leaching efficiency of copper was lower in the combined

reactor than that of the separate reactor due to the change of electrode reactions.

Similarly, a mediated electrochemical oxidation was proposed to recover copper and separate

a rich gold residue from waste PCBs (Fogarasi et al., 2013; Fogarasi et al., 2014). The process was

also carried out by employing two different types of reactors coupled in series, according to the

experimental setup from Fig. 6c. One was a leaching reactor with a perforated rotating drum to

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dissolve base metals, and the other one was a divided electrochemical reactor for the regeneration

of the leaching solution with the parallel electrowinning of copper. In the experiment, the

electrolyte with 0.3 mol/l HCl and different concentration of FeCl3 was prepared with waste PCBs.

Cu in electrolytes HCl and mediators FeCl3 can be generated through electrochemical reaction.

And Fe3+ can regenerate through the anodic oxidation. The electrochemical reactors connected in

series can allow the simultaneous generation of Fe3+ and dissolution of metals without

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supplementation of the leaching agent. The process was evaluated through the dissolution

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efficiency, current efficiency and specific energy consumptions. A 99.04 wt. % high purity Cu at a

current efficiency of 63.84% was gained at a leaching of laboratory scale, and specific energy

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consumption of 1.75 kW h/kg cooper. Electro-oxidation leaching copper in sulfuric acid solution

was also studied for metal powders from waste PCBs (Ping et al., 2009). The experiment tried to

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recover base metal copper by leaching process using H2SO4, NaCl, CuSO4 and the air. In the
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leaching system, chloride ion was taken as complex agent, and Cu2+, air were taken as oxidants.

The result showed that the leaching rate of copper can reach 100%. Oishi et al. (Oishi et al., 2008)
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improved this process. The impurities in the solution were removed by solvent extraction using

LIX 26, and the purified Cu(I) solution was electro-won in a diaphragm cell.
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Electrorecycling is a technology which utilizes minimal chemical input to dissolve and

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recover metals on a cathode for further processing (Lister et al., 2014). The advantage of this

process is that use a single electrochemical cell to maximize energy efficiency. A diagram of the
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electrorecycling system is shown in Fig. 6d. The electrorecycling process generated oxidizing

agents at anode to dissolve metals from the scrap matrix meantime dissolved metals were reduced
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at the cathode. The electrochemical cell configured a trough with the cathode solution. E-pH
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diagrams and the data of metal dissolution were presented for anticipated conditions in the

electrorecycling system. In their work, two stages of electrorecycling were proposed. Firstly Cu,

Sn, Ag and magnet materials using Fe3+ were dissolved in sulfate and then Pd and Au were

dissolved using Cl2 in an HCl solution. Over 95% Cu and Ag were recovered, but the recovery rate

of Au and Pd was low.

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Fig. 6. Schematic diagram of (a) separate reactor consisted of an electrolytic cell for chlorine
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generation (b) combined reactor consisted of an electrolytic cell for chlorine generation (c) a
mediated electrochemical oxidation (d) electro-recycling system (Fogarasi et al., 2014; Kim et al.,
2011a; Kim et al., 2011b; Lister et al., 2014)
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4.5. Supercritical technology

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In recent years, supercritical technology is introduced as an environment-friendly method to

decompose organic polymers and recycle metals due to its special properties, such as low
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viscosities, high mass transport coefficient, high diffusivity, and high solubility for organics

(Matsumoto and Oshima, 2014; Xiu et al., 2015; Zhu et al., 2012).
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Li et al. (Li and Xu, 2015) applied supercritical water (SCW, Tc=374 C, Pc=22.1 MPa) to
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decompose brominated epoxy resin (BER) from waste memory module and environmental

friendly recover metals. Fig. 7a shows the schematic diagram of the semibatch-type reactor.

Experiments were carried under external-catalyst-free with temperatures 350-550 C, pressures

25-40 MPa, and reaction times 120-360 min in a semibatch-type reactor. The results showed that

BER could be quickly and efficiently decomposed under SCW condition, and the recovery rate of

metal reached 99.80%. The mechanism was possibly free radical reaction.

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Supercritical methanol (SCM, Tc=240 C, Pc= 8.09 MPa) to simultaneously recover polymers

and metals from waste PCBs was conducted by Xiu et al. (Xiu and Zhang, 2010). Their study

focused on the characteristics of both oils and solid products obtained from the SCM treated waste

PCBs. Fig. 7b shows the schematic diagram of the chemical recovery process from waste PCBs

using supercritical methanol. The waste PCBs were put into the reactor with methanol of

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appropriate volume. After SCM reaction, the liquid-solid mixture in products was filtered by a

membrane filter with pore size 1.0 m. High concentrations of Cu (34%), Fe (7.9%), Sn (7.9%), Pb

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(6.3%) and Zn (2.6%) were found in most of the solid products when waste PCBs were

concentrated effectively after SCM treatment. A rotary evaporator was used to recover the solvent

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methanol, and then the oil and gas products were also recovered. Besides supercritical methanol,

other supercritical fluids were also employed for the recycling of waste PCBs. Sanyal et al.

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(Sanyal et al., 2013) used supercritical CO2 as solvent with an additional small amount of water to
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recover copper foil, glass fiber and polymer in waste PCB.

A technology of supercritical water oxidation (SCWO) combined with electrokinetic (EK)

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process was developed to recover metals (Xiu et al., 2013, 2015; Xiu and Zhang, 2009a, b). In the

process, the PCBs was pretreated in supercritical water, and then subjected to EK process (Fig. 7c,
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d). Xiu et al. used this technology to recover Cu, Pb (Xiu and Zhang, 2009b) and to prepare Cu2O
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nanoparticles (Xiu and Zhang, 2012) from waste PCBs. In the SCWO treatment experiments, the

sample and distilled water were employed, and hydrogen peroxide (H2O2, 30 wt. %) was used as
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the source of oxygen. The EK process relied upon an electric field with 20 ml of 1 mol/l HCl

solutions added to the SCWO-treated waste PCBs. The metal ions or ionic complexes were
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formed and migrated to the cathode or anode. Experimental results showed that supercritical water
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oxidation (SCWO) process was strong enough to decompose the organic compounds of waste

PCBs, and XRD spectra indicated that copper and lead were oxidized to CuO, Cu2O and PbO2. In

the EK process, Cu and Pb can form complexes with Cl and the complexes can be positively

charged, negatively charged or uncharged (MeCl+, MeCl2 (aq), MeCl3

and MeCl42). The

recovery percentages of copper and lead under optimum SCWO+EK treatment conditions were

around 84.2% and 89.4% respectively.

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Highly uniform and monodisperse Cu2O nanoparticles were gained successfully from waste

PCBs in EK process. The average size of Cu2O nanoparticles decreased from 49.5 to 18.2 nm

when current density increased from 10 to 20 mA/cm2, and the size uniformity of nanoparticles

was improved significantly at a higher current density. Up to 90 wt. % of Cu in waste PCBs could

be recovered as Cu2O nanoparticles under optimized condition.

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Fig. 7. Schematic diagram of (a) semibatch-type SCW reactor (b) SCM recovery process (c,
d) SCW combined with EK process (Li and Xu, 2015; Xiu and Zhang, 2009b, 2010, 2012)
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4.6. Vacuum metallurgical technology

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In recent years, vacuum metallurgical technology has been applied to recover metals from

WEEE because of no wastewater pollution. The separation of metals is based on the difference of

vapor pressure of these metal elements at the same temperature (as shown in Fig. 8a). Under the

guidance of separation criterion, different metals can be successfully separated and recycled from

several waste PCBs. Vacuum distillation of metals is considered to need to experience four crucial

processes, namely, heat transfer, evaporation, mass transfer and condensation. Volatile metals in

interior of the melt spread to the surface and arrive at the boundary layer. The temperature and

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pressure of volatile metals is Tv and Pv. And then the metals begin to evaporate. They are

condensed at condensation wall, which the temperature and pressure of volatile metals decrease to

Tk and Pk. Fig. 8b shows the process of metal from volatilization to condensation. In the process,

the rates of volatile metals can be described different mathematics model (Bird, 2002; Li et al.,

2013).

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Fig.8 (a) migration process of the metals from the melt (b) relationship between the saturation
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pressure and temperature of metals

Zhan et al. (Zhan and Xu, 2009, 2011, 2012; Zhan and Xu, 2008) carried out a series of
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studies on recycling metals from waste PCBs by vacuum separation, using the self-made vacuum
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furnace (as shown in Fig. 9a). The study indicated that Cd can be evaporated preferentially, and

subsequently Zn can be separated as a result of their huge vapor pressure gaps. Mixed metal
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particles of Zn, Cd direct sublimated by solid state and surface oxidation film can hamper this

evaporation process. The separation of Pb was more difficult because the Pb-Bi alloy was formed
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with a low vapor pressure. And Pb was also found in the solders of waste PCBs due to form of
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Pb-Sn alloy.

Vacuum metallurgy can also be used to get metal nanoparticles. Synthesis of bismuth

nanoparticles was systematically investigated following mechanism of aerosol nucleation,

condensation and coagulation. Fig. 9b shows a schematic of the jet aerosol flow condenser unit.

Bismuth vapor was produced in an externally heated tube flow condenser containing a crucible

with the Bi melt. Transport of the vapor in an argon carrier gas jet was followed by rapid

quenching with second argon streams (in a diluter) and by particle collection on a filter. The

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results showed that rapid quenching of the Bi-vapor flow produced particles with narrow size

distribution. In contrast, counter flow quenching resulted in early particle formation and broad

particle residence time distributions producing particles with a wide size distribution. Bismuth

nanoparticles were synthesized through this process, which average diameter was about 12-37 nm

(Wegner et al., 2002). On the basis of Karsten Wegners study, Xing et al. (Xing and Zhang, 2011)

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investigated a novel process for lead nanopowder synthesis from the waste cathode ray-tube

funnel glass.

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Lin et al. (Lin and Qiu, 2011) tried to use the vacuum reduction technology to recover Pb in

waste lead storage battery. They recovered Pb from two parts: metallic grids and lead pastes. The

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results showed that Pb could be satisfactorily recycled. Similarly, the vacuum reduction

technology also was used to recover Pb (about 20-30% PbO) (Mar et al., 2006) in cathode-ray

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tubes (CRTs). Chen et al. (Chen et al., 2009) studied lead recovery efficiency, optimizing of this
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process and the evaluation of environmental safety of the product. A reaction equation was shown:

PbO + C = Pb(g) + CO(g) (9 )

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G T = 289427 - 481.88T + 2RTlnp(328 - 885 C)

The experimental condition was that temperatures were 600-1000 C, vacuum pressures were
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10-10,000 Pa, carbon adding amounts were 0-9%, and holding times were 0.5-6 h, respectively.
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Lead, with a purity of 99.3%, was successfully separated and recovered. The test of Toxicity

Characteristic Leaching Procedure (TCLP) indicated that lead from the foam glass leached at
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optimum conditions was below the regulated value. Besides, the waste Ni-Cd batteries recycling

were also investigated (Huang et al., 2009b, 2010).

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For the recovery of rare and precious metals from WEEE, He et al. (He et al., 2014) adopted
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coke powder as the reducing agent to get metallic indium from discard liquid crystal display (LCD)

panels. In2O3 can be reduced to metallic indium under high temperature condition with reducing

atmosphere. The reactions can be expressed by follows the equation:

ln2O3 + 3C = 2 ln(s) + 3CO( g ) (10)

The experiment for the recovery of indium from waste LCD power showed that the best

parameters were confirmed as 1223 K and 1 Pa with 30 wt. % carbon addition for 30 min and the

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recovery rate of indium could reach to 90 wt. %. On the basis of vacuum carbon-reduction, an

efficient rough vacuum-chlorinated separation method was proposed for the recovery of indium

from waste LCD panels. NH4Cl was used as the chlorinating agent. Fig. 9c shows the schematic

illustration of the vacuum-chlorinated separation. The results indicated that the reaction condition

of vacuum-chlorinated metallurgy was easier than the reaction of vacuum carbon-reduction. The

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reactions can be expressed by follows the equation:

ln 2 O3 + 6 HCl = 2 ln Cl 3 + 3 H 2 O ( g ) (11)

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The weight ratio of NH4Cl to glass powder and the optimum particle size were confirmed as 1:2

and less than 0.13 mm, at 400 C respectively. Indium chloride was successfully recovered from

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the waste LCD panels using this method. The recovery rate of indium and the purity of indium

chloride was 98.02 and 99.50% respectively (Ma et al., 2012).

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Pyrolysis technology can be considered as an alternative technology of recycling WEEE in
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recent years. Pyrolysis can remove non-metallic materials from WEEE, and then metals can be

recovered (Alston et al., 2011; Hall and Williams, 2006). Zhou et al. (Zhou and Qiu, 2010; Zhou
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et al., 2011) has introduced two-step vacuum pyrolysis processes to recycle metals from waste

PCBs. One process was to separate the solder of the waste PCBs firstly, which was molten in the
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heated diesel oil and separated by centrifugal separation; and then used vacuum pyrolysis to
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recover the waste PCBs without solder. The other process pyrolyzed the waste PCBs under

vacuum condition firstly; and then the obtained pyrolysis residue was heated under vacuum to
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recover the solder by centrifugal separation. The vacuum pyrolysis was carried out on the

self-made equipment, as shown in Fig. 9d. The equipment consisted of electromotor, reactor,
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rotating drum, temperature controlled furnace, cold trap, vacuum pump, etc. The rotating drum
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was designed especially to recover solder from waste PCBs. In pyrolysis process, the solder of

waste PCBs was separated and recovered when the temperature range was 400-600 C, the

rotational speed was maintained at 1000 rpm, and the rotating drum was rotated for 10 min. The

recovered solder can be reused directly. The pyrolysis residues containing other metals, glass

fibers and other inorganic materials still need further treatment.

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Fig. 9. Schematic illustration of (a) vacuum distillation recovery system (b) aerosol flow
condenser with its Inconel pipe (c) vacuum-chlorinated separation system (d) vacuum pyrolysis
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process (Ma et al., 2012; Xing and Zhang, 2011; Zhan and Xu, 2009; Zhou and Qiu, 2010)

4.7. Other novel technologies

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Some new technologies such as ultrasound technology (Fengchun et al., 2009),

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mechanochemical technology (Chen et al., 2010), and combination with pyrometallurgy and

hydrometallurgy technology (Havlik et al., 2011; Havlik et al., 2010) also have been tried to
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recycle metals from WEEE.

The technology of ultrasound was applied in recycling metals. Recover the copper and iron
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from waste PCBs sludge by ultrasonically assisted acid leaching. The ultrasonically assisted
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leaching experiment device is shown in Fig. 10a. Sample was pretreated firstly, which was put

into a beaker with water and 30% of H2O2, and stirred at a speed of 300 rpm for 60 min at room

temperature (25 C). Lime was put into sample and then the slurry was filtered. The solution of pH

was adjusted to below 1.5. The result demonstrated that this method can effectively separate

copper from iron, which the leaching rates of copper and iron were enhanced with increasing of

ultrasound energy were reached at 93.76% and 2.07% respectively (Huang et al., 2011; Xie et al.,

2009).

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The mechanochemical method can make technically feasible the recycling of metals from

some specific wastes, such as CRTs funnel glass. Tan et al. (Tan and Li, 2015) provided a

systematic review of the utilization of mechanochemistry in metal recycling the wastes from the

effect of mechanochemical methods to discuss the physicochemical changes, reactions occurred

during these processes, and analyze its mechanisms (as shown in Fig. 10b). Mechanochemical

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technology can be used as a means of pretreatment, and then hydrometallurgical technology to

recycle metals. Through this way, the recovery rate of metal was significantly higher than ordinary

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hydrometallurgy.

Molten salt oxidation (MSO) technology to recover metals in waste PCBs has been proposed

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and this method was efficient for recovering a copper-rich metallic fraction (Flandinet et al., 2012).

Molten salts and specifically molten KOH-NaOH eutectic was used to dissolve glasses, oxides and

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plastics in waste PCBs without oxidizing the most valuable metals. The molten salt was selected a
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mixture of hydroxides, specifically NaOH-KOH, with eutectic composition (Tmelting =170 C). The

experimental setup, as shown in Fig. 10c, consisted by a stainless steel cell and gas inlet through
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by pure argon and iron melting-pot. Crushed waste PCBs samples were placed in an iron melting

pot containing the salt. Non-metallic components, such as fiberglass, epoxy resin were dissolved
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in the molten KOH-NaOH eutectic at 300 C. The metallic fraction which contained copper and
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all the precious metals, were recovered with no dissolution or melting phenomena.

A combined pyro-hydrometallurgical method to treat the printed circuit boards from used
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computers was studied for copper and tin extraction. The samples after thermally pretreated were

leached in the solution of 1 mol/l HCl at 80 C. Fig. 10d is the apparatus for thermal treatment and
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the leaching apparatus. The results showed that the significant increase trend of the copper
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extraction for burned samples compared with unburned samples. After burning process, metallic

copper changed into the copper oxides. The copper oxides were well leached in the hydrochloric

acid, and this is the reason why the cooper was leached out from burned samples. Unlike copper,

after burning, SnO2 can be formed and was minimally leached in HCl. Hence, the leaching had not

too much changed before and after burning process (Havlik et al., 2011; Havlik et al., 2010).

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Fig. 10. Schematic illustration of (a) ultrasonically assisted leaching technology (b)
mechanochemical technology (c) molten salts leaching technology (d) combined
pyro-hydrometallurgical technology (Flandinet et al., 2012; Havlik et al., 2011; Tan and Li, 2015;
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Xie et al., 2009)

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5. Environmental and practical defects of advanced technologies

As described in section 4, all of these methods and technologies have been improved and
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upgraded on the basis of traditional methods.

Pyrometallurgy can recycle some base metals such as Cu, Pb, Zn etc, and these metals can be
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gained with high purity through smelting, refining process. Advanced pyrometallurgical
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technology firstly adds the mechanical-physical pretreatment of WEEE. In addition, it pays great

attention to the treatment of waste gas during metals smelting and refining processes. However,

although pyrometallurgy has been improved furthest, some pollution problems are still inevitable.

For example, atmosphere pollution resulted from fine particles PM2.5 and PM10 or the release of

some toxic gas, such as dioxins and furans should be considered. Moreover, the equipments are

expensive, consume a vast amount of energy, and not suit for small and medium-sized enterprises.

Moreover, the equipments are expensive, consume a vast amount of energy, and not are suitable

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for small and medium-sized enterprises. More importantly, the pyrometallurgical technology has

limitations in recycling the single metal from rare and precious metals.

Some modified hydrometallurgical technologies, such as mild extracting technology,

electrochemical technology are designed with the main purpose to solve the problem of the single

metal recycling, and it has good performance in terms of recovery ratio and purity. However, there

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are still some defects and shortages to be improved. Take non-cyanide leaching methods to

recover precious and valuable metals for example. Most of non-cyanide lixiviants are low cost and

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environment-friendly, but has low chemical stability with low metal recovery. In addition, for

thiourea leaching, an above 90% recovery rate can be gained in a short leaching time, yet the

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thiourea consumption would be too high and very expensive compared to cyanide lixiviant.

Biometallurgy has too many limitations: Certain microorganism treats specific metal; and the

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kinds and content of recycling metal by biometallurgy also are limited. Electrochemical
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technology is an environment-friendly technology, but the sludge generating through this process

is hazardous waste. Disposing of sludge is complicated and difficult. For supercritical technology,
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although it can effectively decompose organic substances from WEEE, remaining metals mixture

still need to be further separated through hydrometallurgical technology or other technologies. In

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addition, generated liquid phase and gas through supercritical process also have a negative impact
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on environment to a certain extent. For example, liquid phase contains a significant number of

phosphated compounds and phenol derivatives.

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The environmental and economic benefits of vacuum metallurgical technology for recycling

WEEE have been validated. In some industrial practices, gas flow can be effectively controlled
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and no wastewater discharge or dust emission occurs. This technology is an environment-friendly

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and promising method for recycling metals from WEEE. However, it still needs to be improved

for further promotion. On the one hand, vacuum metallurgical technology has obvious advantages

for low boiling point, high saturation vapor pressure base metals separation, such as Zn, Pb, and

Cd. On the other hand, the separation effect for rare and precious metals which have low saturated

vapor pressure such as Au, Ag through vacuum distillation method is not perfect. In addition,

whether it can meet the industrial standard for metal purity after the separation should be

investigated. There are also some theoretical issues waiting for further research before its

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industrial application, according to the review of Zhan (Zhan and Xu, 2014). Table 6 shows the

status of these technologies of recycling metals from WEEE.

In fact, almost all efforts from new technologies aim to achieve better cost-effectiveness,

environmental promotion and sustainability. With the continuous improvement and development

of recycling technologies, the researchers have begun to focus on new technologies which have

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small harm to the environment and human. As a result, some combinative recycling technologies

should be put forward to improve recycling of the metals from WEEE.

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Table 6 Status of all kinds of technologies of recycling metals from WEEE (Akcil et al., 2015; Cui and Zhang, 2008; Hadi et al., 2015b; Tan and Li, 2015;
Zhan and Xu, 2014)

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State of Species and effect of Advantages of environmental and Disadvantages of environmental and
Recycling technology
recovery metals recovery metals technological aspect technological aspect

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totally-commercial; owing some dust vast cost of investment; fine particles pollutions;
almost all metals; high
Pyrometallurgical technology pure solid metals chamber and exhaust gas treatment consuming a vast number of energy; difficult to
recovery rate;
plant recovery of precious metals

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almost all metals; recovery low toxicity; simple and easy
high cost of some reagent; some reagents could
Mild extracting technology solution rate related to the reagents accessibility; relative low
result in waste water pollution; semi-commercial;
and reaction condition environment damage;

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only for a few specific

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metals; considerable environment-friendly; low cost of high selectivity of metals (only for a few specific
Biometallurgical Technology solution
recovery rate for Cu, Zn, investment; metals, such as Cu, Zn, Au); no industrialization;
Au etc.

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only for specific metals; high recovery efficiency; low cost of waste water and residue pollution; low
Electrochemical technology pure solid metals
high recovery rate; investment; mature technology; industrialization;

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solid mixture of almost all metals; high high recovery efficiency; low cost of failure to recycle single metal; waste oil and
Supercritical technology

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metals recovery rate; investment; low environment damage waste gas pollution; low industrialization;

only for high vapor

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Vacuum metallurgical environment-friendly; short relative high cost of investment; low
solid single metal pressure metals; high
Technology technological process; industrialization; immature technology
recovery rate;
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Other metallurgical technologies need to combined with

solid mixture of environment-friendly; low cost of failure to recycle single metal; no
(ultrasonical, mechanochemical other technologies to
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metals/solution investment; industrialization;

technology etc) recycle metals;

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6. Perspectives on recycling technologies

6.1. Recycling technologies aspect

After a decade of effort, the recycling technologies for metals from WEEE have gained

obvious improvement. However, it is no denying that current technologies still have some

challenges for further promotion. For example, these new and novel recycling processes for metals

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are relatively single and dispersed. They are difficult to independently and efficiently separating

metals from WEEE.

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There are three considerations that ought to be noticed and ensured for the future recycling

technology innovation: (1) Technologies in the future should be prepared to face

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commercialization, and suit for small and medium-sized enterprises in terms of investment or

equipment; Further research should focus on the development of pilot scale tests to generate

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operational and cost data with the ultimate aim of commercialization; (2) Single technology
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cannot solve all the problems because WEEE is a complicated system. So, recycling technologies

would be more varied, and technology should be integrated according to the physical and chemical
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properties of all kinds of WEEE; (3) Future technologies should own high separation efficiency,
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recovery rate and greater sustainability.

6.2. Environmental protection aspect

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As reviewed above, developed and modified technologies can successfully recover base

metals, such as Cu, Pb, Zn, Cd and precious metals, such as Au, Ag. Advanced recycling methods
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and technologies also have been improved and upgraded comparing with traditional methods in
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aspect of environmental protection. However, some methods still have negative effects on the

environment.
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There are three considerations that ought to be noticed and ensured for the future recycling

technology innovation: (1) Well-designed pretreatments like removing plastics, papers, irons, etc.

are necessary. For example, a mechanical-physical technology as the means of pretreatment is a

must procedure to separate the metal and nonmetal, in order to avoid the generation of toxic gases

such as PCDD/Fs and residues resulting from non-metals in WEEE; (2) Enterprise or government

should advocate the use of green reagent in recycling processes/technologies to reduce pollution

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of waste water; (3) Comprehensive resource utilization as far as possible for both metals and

nonmetals in WEEE should be the target in recycling processes/technologies.

7. Conclusions

On the one hand, the WEEE can cause serious environmental problems if not be treated

properly. On the other hand, WEEE contains considerable quantities of metal resources. Therefore,

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developing the novel technologies to recycle the metals from WEEE is of great significance from

both economy and environment perspectives. Current status of recovery technologies for metals

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from WEEE are summarized and discussed in detail in this review.

Based on traditional recycling technologies of WEEE, pyrometallurgical technology and

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hydrometallurgical technology have been significantly improved in recent years. Some modified

and mild extracting technologies, such as leaching process of chlorinate, ammonia-ammonium and

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non-cyanide lixiviants can effectively recycled metals from WEEE in aspect of recovery ratio and
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environmental protection. The leaching rate of base metal Cu from WEEE can reach 98%. In the

non-cyanide leaching precious metals Au systems, thiourea, thiocyanate and combining method of
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thiourea-thiocyanate can form stable and soluble complexes of Au(SC[NH2]2)2+, Au(SCN)2,

Au(SC[NH2]2)2SCN etc to extract Au and extraction rate of Au exceeded 70%. In addition, some
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novel and new technologies, such as supercritical technology, vacuum metallurgical technology
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and ultrasound technology etc were put forward in past decade and had also obtained quite

satisfactory results in terms of recycling base and precious metals from WEEE. For example,
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exceeding 80% Cu in PCBs can be recycled by supercritical technology. Vacuum metallurgical

technology can successfully separate Cu, Pb and Zn etc metals in PCBs.

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Although many endeavors about development of recycling technologies have been attempted,
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yet until now there is still a huge room to achieve the environment-friendly and sustainable

recycling for metals. Single technology still has some limitations and can't solve all problems

because WEEE is a complex system. Some combined and integrated technologies have begun to

be put forward. For example, mechanochemical technology can be used as a means of

pretreatment, before hydrometallurgical technology being used to recycle metals (Tan and Li,

2015). Combination of physical processing and selective leaching was used to extract Cu in

WEEE (Silvas et al., 2015). Hence, in the future, some combined and integrated technologies

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should be applied to recover metals from WEEE. We can predict that future technologies are more

efficient, low cost, environment-friendly, and combined with various technologies, such as

physical, chemical, biological, and so on. Just as shown in the flow chart of Fig. 11, an integrated

recycling technology will be presented to recycle metals. The recycling technologies of metals

from WEEE, meeting the requirements of environmental protection and social needs, will be

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realized in the near future.

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Fig.11. A schematic flow sheet showing an integrate recycling technology to recycle the metals from WEEE
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Acknowledgments

This work was supported by the National Natural Science Foundation of China (51534005,

51278293 and 51178262).

Appendix A. Supplementary data

Supplementary data associated with this article can be found, in the online version, at the website.

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Acronyms and Abbreviations

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WEEE waste electrical and electronic equipment

BFR bromined flame-retardant

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Waste PCBs waste printed circuit boards

PMO precious metals operations

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BMO base metals operations
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LIBs lithium-ion batteries

SCW supercritical water

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BER brominated epoxy resin

SCWO supercritical water oxidation

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SCM supercritical methanol

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EK electrokinetic

XRD X-ray diffractometer

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LCD liquid crystal display

CRTs cathode-ray tubes

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TCLP Toxicity Characteristic Leaching Procedure

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MSO molten salt oxidation

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Highlight

Current recovery technologies for metals in WEEE are summarized and reviewed

Defects and shortages of existing technologies are analyzed in detail

Suggestions for technology promotion and environmental protection are presented

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