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Waste Management 96 (2019) 175–180

Contents lists available at ScienceDirect

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

Towards minimization of secondary wastes: Element recycling to


achieve future complete resource recycling of electronic wastes
Lingen Zhang, Zhenming Xu ⇑
School of Environmental Science and Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, People’s Republic of China

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

Article history: Recycling resources from millions of tons of e-wastes are a global challenge. E-wastes is complex and
Received 30 March 2019 contains both toxic organics and valuable metals. Therefore, the technologies for e-wastes recycling
Revised 12 June 2019 are totally different from those used for mineral separation. Current technologies for e-wastes tend to
Accepted 19 July 2019
focus on recycling materials with high economic value and ignore components that cannot be recycled
Available online 22 July 2019
or have low reuse value. As a result, some secondary pollution problems inevitably occur due to the recy-
cling process. Based on these problems, we summarize the universal characteristics of e-wastes and
Keywords:
explore new approaches to achieve complete resource recycling of e-wastes with minimum secondary
Element recycle
E-wastes
waste generation. A concept of element recycling is proposed to achieve complete resource recycling
Waste recycling of e-wastes in the study. We can use the properties of the elements in different types of e-wastes to
Minimized secondary waste achieve e-wastes recycling, i.e., recycle of elements in e-wastes. Under the guidance of element recycling,
various e-wastes types have common connections. If element recycling in e-wastes is realized, all com-
ponents in e-wastes can be fully recycled without/with minimal production of secondary waste. The two
case studies are discussed to clarify the concept and principle of element recycling. This study explores
the recycling of e-wastes from a new perspective—element recycling in e-wastes. The concept of element
recycling is significant for resource recycling from e-wastes.
Ó 2019 Published by Elsevier Ltd.

1. Introduction disposed of in landfills, burned in incinerators, or shipped to devel-


oping countries where rudimentary e-wastes recycling occurs
In the current industrial civilization, electronic products are (Julander et al., 2014; Kim et al., 2015). Environmental pollution
greatly convenient for daily life, but these products result in and threats to human health often occur due to improper handling
the dilemma of the ‘‘junk siege” caused by electronic waste of e-wastes (Ogunseitan et al., 2009). Hence, in the face of the cur-
(e-wastes). E-wastes is ubiquitous with the continual development rent recycling situation, appropriate e-waste recycling is necessary
of information technology and replacement of electronic products. and urgent.
According to the latest research, approximately 40 million tons of In fact, e-wastes is complex and contains both toxic organics
e-wastes was globally generated in 2015, and this amount and valuable metals. Obviously, metals and renewable materials
increased to 47 million tons in 2017 (Singh et al., 2016). Although are still valuable resources in e-wastes (Li et al., 2015; Reck and
e-wastes accounts for only 3–5% of solid waste, its variety and Graedel, 2012). However, plastics, brominated flame retardants
content of valuable metals and plastics are far more than those (BFRs), liquid crystals and other organic matter from e-wastes
of other forms of municipal waste (Li and Xu, 2010). Hence, are harmful. If the e-wastes is not properly disposed or recovered,
e-wastes is worthy of the name ‘‘urban mine”. According to a they will cause serious environmental pollution and even jeopar-
survey by the United States Environmental Protection Agency, dize human health (Sun et al., 2016; Tian et al., 2011). Recycling
recycling valuable resources from e-wastes have significant advan- of e-wastes by environmentally unfriendly, hazardous and primi-
tages, such as the generation of less secondary waste and lower tive technologies in China has increased in the past decades
energy consumption (He and Xu, 2014). However, only approxi- (Ni et al., 2010).
mately 10% of e-wastes is safely recycled, and the remainder is Because of the variation in e-wastes, the methods and technolo-
gies to recycle resources from e-wastes are totally different from
the technologies used for mineral separation. The e-wastes is a
⇑ Corresponding author. complex system that contains various plastics, organic substances
E-mail address: zmxu@sjtu.edu.cn (Z. Xu). and metals. The most of minerals are far less complex than

https://doi.org/10.1016/j.wasman.2019.07.026
0956-053X/Ó 2019 Published by Elsevier Ltd.
176 L. Zhang, Z. Xu / Waste Management 96 (2019) 175–180

e-wastes. The recycling methods of e-wastes need to consider (3) Valuable components and pollutants in e-wastes are rela-
harmless and resourceful comprehensively. Currently, most tive. Researchers tend to recycle materials with high eco-
environmentally friendly and economically viable treatment tech- nomic value, such as metals, but most researchers rarely
niques, including physical separation, pyrometallurgical technol- care about components in e-wastes that cannot be recycled
ogy, mild extraction technology, electrochemical technology and or have a low reuse value. As a result, they fail to explore
vacuum metallurgical technology, focus on recycling valuable complete resource recycling for a certain e-wastes type.
resources (Cao et al., 2016; Kaya, 2016; Zhang and Xu, 2016a). By Hence, some secondary pollution problems inevitably occur.
these means, valuable resources can effectively be recycled. For Therefore, complete resource recycling of e-wastes should
example, a large number of modified and new hydrometallurgical be a goal.
techniques, such as mild extraction technology and electrochemi-
cal technology, were designed with the main goal of solving the 2.2. Concept and achievement of element recycling
problem of single metal recycling from e-wastes, but some envi-
ronmentally toxic and harmful reagents still exist. In addition, Substances on Earth are made up of chemical compounds.
most researchers have not focused on constituents in e-wastes that Elements are the smallest unit of chemical compounds. Chemical
cannot be recycled or have low reuse value. As a result, researchers reactions between substances are reactions between chemical
have failed to explore complete resource recycling for a certain compounds, involving the migration, reaction and transfer of
waste, and some secondary waste is even produced in the process elements. Thus, if the elements in the substances are in a cycle,
of e-wastes recycling. Hence, some secondary pollution problems the substance recycles itself. As described above, e-wastes is com-
frequently occur due to the treatment process. posed of chemical compounds and elements. E-wastes includes
Our team has been committed to studying resource recycling of almost all the elements in the periodic table and can be considered
e-wastes. During more than ten years of research, we have pro- an ‘‘element bank”. If e-wastes is considered an aggregation of ele-
posed various methods and technologies for the treatment of vari- ments, we can redistribute these elements using some integrated/
ous e-wastes types, such as printed circuit boards, toner cartridges, new technologies to form new and useful compounds. Elements in
batteries, refrigerators and liquid crystal display panels. These various e-wastes types can be regenerated by regeneration of
methods and technologies mainly include mechanical-physical elements. The concept is called element recycling in e-wastes.
separation, supercritical fluid, and vacuum metallurgy (Li and Xu, Using element recycling in e-wastes can achieve complete
2015; Ruan and Xu, 2016; Wang and Xu, 2015; Wang et al., 2015; resource recycling of e-wastes; i.e., all chemical compounds from
Zhan and Xu, 2014; Zhang and Xu, 2016b; Zhou and Xu, 2012). As e-wastes are recycled, and no/few residual wastes is generated,
our research has progressed, we have realized that the components under certain conditions. The concept and achievement of element
of e-wastes are complex and disordered, but each component still recycling is showed in Fig. 1. Elements in nature are utilized in the
has its own characteristics. Hence, we must summarize the univer- form of coal, ore, oil, and natural gas. Fossil fuel energy is used to
sal characteristics of e-wastes and further explore and try some produce electronic products, which eventually become e-wastes
new approaches to achieve complete resource recycling of e- after reaching their life span. These e-wastes can be connected
wastes with no/minimal generation of secondary waste. by various elements. Based on the characteristics of e-wastes and
In the paper, a concept of element recycling in e-wastes is first some elements, reaction of redistribution and recombination of
proposed. Then, concrete implementation for element recycling is elements in e-wastes can occur to generate new substances to
clarified in detail. Finally, two case studies are analyzed to explain achieve e-waste recovery. It is meaningful that using the element
the concept of element recycling. In summary, this study is mean- recycling achieves complete resource recycling of e-wastes for
ingful for the sustainable development of resource recycling from the sustainable development of electronic and home appliances
e-wastes. industry.
How can an appropriate element recycling method be found for
2. Theory and methods various e-wastes? Several principles should be clarified to achieve
element recycling in e-wastes. An appropriate element cycle needs
2.1. Universal characteristics of e-wastes to be considered based on the following aspects:

E-wastes is diverse with various chemical compositions. There- (1) The physical and chemical properties of various elements in
fore, we must determine universal characteristics and rules for the e-wastes components should be understood to explore and
unordered components in e-wastes. Several universal characteris- find corresponding recovery technologies. Meanwhile, ele-
tics of e-wastes are summarized as follows: ment characteristics can also be considered to match suit-
able elements. A clear understanding of the element
(1) Composition of e-wastes is complex and varied. The diver- composition and properties of different e-wastes has advan-
sity of e-wastes leads to the complexity of e-wastes recy- tages for choosing appropriate recycling techniques and
cling. E-wastes types may appear to be completely methods to recycle these e-wastes.
different, but in essence they are composed of various ele- (2) The chemical components of e-wastes that can be separated
ments. E-wastes almost includes all elements in the periodic by physical separation technologies to achieve element recy-
table. Hence, elements are a common connection of various cling should be prioritized. For example, according to the dif-
e-wastes types. In addition, because of the complexity of e- ferent physical properties of plastics in the waste print
wastes, the treatment technology should be innovative, inte- circuit boards, some physical methods such as corona elec-
grated and comprehensive. trostatic separation (Li et al., 2008), infrared optical separa-
(2) The components in e-wastes have their own physical and tion (Li et al., 2019) and eddy current separation (Ruan
chemical characteristics, for example, different features et al., 2012) etc. are adopted to recycle plastics environmen-
and metal contents, different types of organic matter from tally. Compared with chemical separation, physical separa-
plastic, and different chemical forms of elements in com- tion technologies are relatively environmentally friendly.
pounds. Even though the components have different proper- (3) If element recycling must be achieved by chemical separa-
ties, a certain similarity may exist among the elements in tion, element recycling from in e-wastes themselves should
these components. be preferentially explored. By element recycling, some new
L. Zhang, Z. Xu / Waste Management 96 (2019) 175–180 177

Fig. 1. Concept, achievement and case studies of element recycling to achieve e-wastes recycling.

compounds will be synthesized. This own element recycling problems of resource recycling in e-wastes. Hence, the new
often regenerates the compound from the e-wastes. Finally, and novel recycling technologies would be more varied,
this own element recycling can maximize the regeneration integrated and comprehensive. These new methods can be
and reuse of e-wastes. For example, in situ reduction reac- proposed based on the physical and chemical properties of
tion of a positive electrode material LiCoO3 and negative the elements in e-wastes. At the micro level, the new and
electrode graphite in a lithium ion battery and a reaction integrated recycling technology should pay more attention
of adding lithium ion for recycling waste lithium ion battery. to the regeneration of the elements in e-wastes.
(4) For chemical separation, if element recycling must be
achieved by adding additional elements, the complementary 3. Results and discussion
addition of elements from other e-wastes is crucial. The add-
ing additional elements can much match the elements in the In this section, two case studies are analyzed to clarify and
e-waste, and it can promote and improve the effect of recy- explain this concept.
cling. Hence, this addition should ensure that the new syn-
thetic compounds have a high added value and high CASE STUDY 1
recovery rate of elements.
(5) A suitable, innovative, comprehensive recycling technology In general, LiCoO2 and graphite are electrode materials in com-
is needed for the implementation of element recycling in mercial lithium-ion batteries. A mechanical scraping was used as
e-wastes. With the increasing complexity of electronic to gain mixed powder containing LiCoO2 and graphite powders.
products, single recycling technology is hard to solve the Fig. 1 shows an integrated method of oxygen-free roasting-wet
178 L. Zhang, Z. Xu / Waste Management 96 (2019) 175–180

magnetic separation to in situ recycling of cobalt, LiCO3 and gra- Co, C, and O in the mixed electrode material were regenerated.
phite (Li et al., 2016). In this recycling process, we adopted element Hence, element recycling of LiCoO2 in ion batteries is achievable.
recycling from lithium-ion batteries to recycle resources. LiCoO2 This process was further expanded to recycle lithium ion ternary
and graphite powders were transformed into cobalt, LiCO3 and batteries. An integrated process was proposed to recycle LiCoO2
graphite. from spent LIB, as shown in Fig. 2(C). Firstly, the cathode and anode
Fig. 2(A) showed the situation of thermal weightlessness for the materials were crushed and mixed by mechanical separation. Then,
different mole ratio of LiCoO2 and C (samples #1–3: mole ratio n the oxygen-free roasting process was adopted to damage the
(LiCoO2):n(C) = 1:0, 4:3 and 4:18.3) under the condition of air lithium oxides. Li was released at a certain temperature. Finally,
atmosphere. An obvious weight loss for sample #2 and sample high-value Li2CO3 was recycled by water leaching and evaporating.
#3 occurred at 600–800 °C, indicating a LiCoO2 reduction reaction The graphite in the filters was burned away to obtain the precur-
occurred in this stage. The mass loss of sample #2 and sample #3 sors of cathode materials (Xiao et al., 2017).
was 7.61 wt% and 32.97 wt%, respectively under exceeding reac-
tion temperature 800 °C. The results indicated that oxygen-free CASE STUDY 2
roasting could feasibly reduce LiCoO2. When the material is fully
roasted, the residue products were still in a mixture with low PVC plastic (containing C, H, and Cl) and stripping products
value. Further separation can achieve the purification of products. from waste liquid crystal display (LCD) panels (containing In, C,
The crystal structure of products was identified by X-ray diffrac- H, and O) in e-waste are seemingly unrelated. However, these
tion (XRD, D8 ADVANCE, BRUKER, Germany) with Cu Ka radiation. two different types of wastes have a connection under the guid-
All the measurements were repeated three times, and only the ance of element recycling. A mechanical stripping separation was
mean values were reported. The XRD results of the residue after first adopted to obtain a stripping product that can concentrate
roasting and the ferromagnetic material obtained after wet indium and liquid crystals from LCD panels. As shown in Fig. 1, a
magnetic separation are shown in Fig. 2(B). The results showed vacuum pyrolysis and chlorination process was developed to
that only the cobalt peak is observed in the ferromagnetic material, recycle indium from LCD panels. In the process, PVC plastic from
indicating that the cobalt powder was enriched by the process. By e-wastes was used as chlorinating agent. With the recycling of
the measurement of ICP-AES, the content of Co was 97.68 wt%. In indium as form of InCln, the C, H and O in PVC plastic were reused
this element recycling process, the recovery rates of Co, Li and gra- to generate prepare a carbon coating and energy products (Zhang
phite were 95.72%, 98.93% and 91.05%, respectively. Almost all Li, and Xu, 2017).

Fig. 2. (A) Thermogravimetric analyses of different mole ratio of LiCoO2 and C (samples #1–3: mole ratio n(LiCoO2):n(C) = 1:0, 4:3 and 4:18.3) in air atmosphere; (B) XRD
results of the residue obtained after roasting and wet magnetic separation; (C) The integrated process of recycling LiCoO2 from spent LIBs (Li et al., 2016; Xiao et al., 2017).
L. Zhang, Z. Xu / Waste Management 96 (2019) 175–180 179

The stripping product, a certain proportion of polyvinyl chloride cling process because some recycling process could exist environ-
(PVC) plastic and a 13X molecular sieve were placed in a vacuum mental risk. In order to specify the environmental risk indicator it
furnace to produce a vacuum pyrolysis reaction. Thermogravimet- was felt appropriate to consider the environmental impacts of
ric mass spectrometry (TGA-MS) analysis was used to explore the these recycling process through the use of Life Cycle Assessment
feasibility of C, H, Cl, and In recycling via vacuum pyrolysis of PVC (LCA), which is based on the listing and quantification of all flows
plastic (as shown in Fig. 3a). We can see clearly that two significant coming in and out of the system considered, including extraction,
weight losses happened in the range of 513–723 K. The simultane- processing, transport, end-of-life recycling, etc. Meantime, collec-
ous MS results (Fig. 3b) showed gaseous HCl and ethylene were tion and recycling channels of the end-of-life products should be
produced in the process. The Cl in PVC plastic combined with the broadened to become more unblocked. For example, the govern-
In in the LCD panels and was regenerated in the form of InCl3, ment can encourage recycling of end-of-life products by imple-
evaporated in the condensing zones and collected as a condensate menting subsidies for the recycling enterprises. To sum up, a
product (Fig. 3c). InCl3 was the main indium chloride in the con- green industrial chain of circular economy for the process of
densed products base on the analysis of XPS analysis. In addition, exploitation, extraction/refining, manufacture and recycling need
the carbon coating and energy products can be produced by the to be focused and emphasized.
transformation of C, H and O elements in PVC plastic. The SEM
image showed that the carbon coating was formed by crosslinking 4. Conclusion
of various carbon chains. The formation mechanism was that the
pyrolytic oil and gas such as alkanes, olefines and alkyl acids pro- The diversity of e-wastes leads to the complexity of e-wastes
duced in the pyrolysis process can occur the adsorption, breaking recycling. E-wastes not only contains valuable resources but also
of chemical bonds cross-linking and carbonization. Finally, the contains harmful components, such as some types of organic mat-
coated carbon fiber molecular sieve was formed. Exceeded 98% ter. As we all know, e-wastes types have their own chemical com-
can be recycled at the optimized conditions. In this process, simi- positions and elements. E-wastes include almost all elements in
larities among elements are adopted to achieve complete resource the periodic table and can be considered an ‘‘element bank”.
recycling through the coordinated treatment of two kinds of Elements in nature are applied in various electronic products.
wastes—PVC plastic and waste LCD panels from e-wastes. These electronic products eventually become e-wastes. Various
In addition, for the aspect of management of recycling, types of e-waste can be connected through the elements. It is fea-
strengthening government regulation is necessary for some recy- sible to realize complete resource recycling of e-wastes by utilizing

Fig. 3. (a) Thermogravimetric situation for the pyrolysis process of PVC by TGA-DTG analysis; (b) Mass spectrometry analysis of HCl and C2H4 in pyrolysis process of PVC; (c)
In 3d spectra of the stripping and condensed products by XPS analysis and (d) SEM image of the molecular sieve at 1073 K (Zhang and Xu, 2017).
180 L. Zhang, Z. Xu / Waste Management 96 (2019) 175–180

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