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Authors Accepted Manuscript

A thermodynamic-based life cycle assessment of


precious metal recycling out of waste printed
circuit board through secondary copper smelting

Maryam Ghodrat, M Akbar Rhamdhani, Geoffrey


Brooks, Maria Rashidi, Bijan Samali
www.elsevier.com/locate/envdev

PII: S2211-4645(17)30009-X
DOI: http://dx.doi.org/10.1016/j.envdev.2017.07.001
Reference: ENVDEV362
To appear in: Environmental Development
Received date: 20 January 2017
Revised date: 7 July 2017
Accepted date: 10 July 2017
Cite this article as: Maryam Ghodrat, M Akbar Rhamdhani, Geoffrey Brooks,
Maria Rashidi and Bijan Samali, A thermodynamic-based life cycle assessment
of precious metal recycling out of waste printed circuit board through secondary
copper smelting, Environmental Development,
http://dx.doi.org/10.1016/j.envdev.2017.07.001
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A thermodynamic-based Life cycle assessment of precious metal
recycling out of waste printed circuit board through secondary
copper smelting

*
Maryam Ghodrata , M Akbar Rhamdhanib, Geoffrey Brooksb, Maria Rashidia, Bijan Samalia

a
Centre for Infrastructure Engineering , School of Computing, Engineering and Mathematics, Western
Sydney University, Sydney, Australia
b
Department of Mechanical Engineering and Product Design, Swinburne University of Technology,
Victoria, Australia

m.ghodrat@westernsydney.edu.au

Mariam.godrat@gmail.com
arhamdhani@swin.edu.au

gbrooks@swin.edu.au

m.rashidi@westernsydney.edu.au

B.samali@westernsydney.edu.au

*
Corresponding author. Tel.: +61247360106; fax: +61 2 4736 0054

Abstract

This study provides an environmental impact assessment of the black copper smelting route for the

processing and recovery of copper and other valuable metals such as gold and silver from waste

printed circuit boards (PCB). Thermodynamic based analysis was conducted to simulate the recycling

process and a life cycle assessment was carried out to estimate and compare the environmental impact

of the two scenarios: (1) recycling of precious metal out of waste PCBs through secondary copper

smelting (Electronic Waste Processing, EWP); and (2) secondary copper recycling without adding

electronic waste to the feed (SCR). The results of the study revealed that environmental impacts of
using e-waste along with low-grade copper scrap in existing smelters to recover precious metals are

dependent on the distance the material feed travels to the smelter and the means of electricity

supplying the smelter. It is also found that the impact of the EWP scenario for climate change,

freshwater eutrophication, and fossil depletion is significantly higher than those obtained from the

SCR scenario and it is mainly because the metal and oxide dust in former scenario needs to be further

refined to recover metals such as nickel, zinc and lead. The results also confirm that 10% cut in

electricity usage in EWP scenario, has the higher environmental benefit in almost all dominant

categories.

Keywords: Life cycle assessment, Precious metal recycling, Waste printed circuit boards, Secondary

copper smelting

1. Introduction

Electronic waste (e-waste) is chemically and physically distinct from other forms of municipal or

industrial waste; it contains both valuable and hazardous material that require special handling and

recycling methods in avoiding environmental contamination and detrimental effects on human health.

Recycling can recover reusable components and base metals, especially copper (Cu) and other

precious metals. In 2006, the world's production of e-waste was estimated at 20 to 50 million tonnes

per year (UNEP, 2007), representing 13% of the global municipal waste production of 1,636 million

tonnes per year (OECD, 2008). Cobbing (2008) calculated that computers, mobile telephones and

television sets would contribute 5.5 million tonnes to the e-waste stream in 2010, rising to 9.8 million

tonnes in 2015. In rich countries, e-waste constitutes around 8% of municipal waste by volume

(Widmer et al., 2005). The chemical composition of e-waste differs subjected to the age and type of

the waste item. However, most e-waste contained a mixture of metals, particularly Cu, aluminium
(Al) and Iron (Fe), shielded with, or mixed with different types of plastics and ceramics (Hoffmann,

n.d.). An unwanted personal computer with a CRT monitor normally weighs 25 kg and composes of

metal (43.7%), plastics (23.3%), electronic components (17.3%) and glass (15%) (Berkhout and

Hertin, 2004). Heavy waste electronic items, such as washing machines and refrigerators, which

mostly consist of steel, may have lower potential environmental pollutants than lighter electronic

waste items, such as laptop computers, which may encompass high concentrations of flame retardants

and heavy metals (Robinson, 2009). Nearly all electronic waste comprises some valued components

or base materials, particularly Copper, Silver and Gold. A recent economic analysis conducted by

(Ghodrat et al., 2016) confirmed the considerable potential value of e-waste recycling that should be

taken into consideration. According to a survey carried out by Davis and Herat (2008) very limited

audit data relating to the composition of e-waste within the domestic waste stream exists in Australia;

also very few facilities can handle the processing or recycling of e-waste. This is further multiplied

by large geographical distances between many of the major metropolises and the treatment spots.

Davis and Herat (2007) hence concluded that e-waste reprocessing is only environmentally and

economically viable in larger cities in Australia where demand is high. Lately a set of new legislation

for the disposal and handling of e-waste in Australia developed using the European Union (EU)

directive as a basis which takes into consideration factors unique to the Australian situation.

Basically the concentration of precious metals in waste PCBs is higher than the concentration of

precious metals in their ores (Chancerel et al., 2009). Based on the research done by Hagelken et al.,

(2005), currently mined ores for the extraction of gold and palladium include less than 10 g/t of

precious metals compared to the concentrations of the similar metals in PCBs of personal computers

(250 g/t of gold and of 110 g/t of palladium). On the other hand, the extraction of precious metals

through mining is associated with negative environmental impacts through significant emissions of

greenhouse gases and energy, water, and land usage (Ayres 1997). Additionally, the environmental

impact of informal recycling of valuable metals out of e-waste especially in undeveloped countries

could be critical and may lead to human health risk.


Based on the research conducted by (Morf et al., 2007) on the component concentrations from Swiss

e-waste, it was revealed that concentrations of Cd, Cu, Ni, Pb and Zn released into the environment

would pose a risk to the ecosystems (Widmer et al., 2005) and the potential hazards of persistent

inorganic and organic contaminants (such as toxic PCBs, Polybrominated diphenyl ethers (PBDEs),

and metals) to the ecosystem are expected to persist for many years. There is limited information,

however, on the impact of e-waste processing through secondary metal scrap recycling on

environmental and human health. In this regards, this paper aims to explore the environmental

consequences of alternatives for recycling high-grade waste PCBs through black copper smelting

route (a secondary copper production process). The motivation for this is to replace a portion of the

secondary copper (low-grade copper scrap) with waste PCB scrap. This can further increase the utility

of existing plants without the need to invest capital in new installations and at the same time, moves

toward forming a close-loop for copper therefore the environmental consequences of replacing a

proportion of secondary feed in existing smelters in Australia are also explored in this paper. Life

cycle assessment (LCA) is an analytical tool for quantifying resource consumption and environmental

impacts linked to a product, process or activity during its entire life cycle. The purpose of most LCA

studies is to find the design option that minimises the life cycle impact of the process.

A substantial body of research on the life-cycle analysis of energy usage and environmental impacts

of metals is available from various life cycle inventory (LCI) databases (Classen et al., 2009,Althaus

and Classen, 2005, Althaus et al., 2007, Design, 2012). Yet, many LCI data are reported in an

aggregated form and hence makes it challenging to make vigorous comparisons or taking co-

production matters into account. A research carried out by Nuss and Eckelman (2014) overcome this

issue to some extent by reviewing existing metals inventory data and collection of new data for

several elements. Their results showed that for the majority of elements in their metallic form, the

cradle-to-gate environmental burdens are largely a result of the purification and refining stages. On

the other hand the criticality of different metals used in modern technologies is an area of growing

interest. For example criticality of metals recycling as an environmental risk alleviating technique

addressed in the work of Graedel et al.(2015) and the European Union report of the Ad hoc Working

Group on defining critical raw materials (Commission, 2014). In an effort to bring enhanced rigor
evaluation of metallic resource recycling, in this paper we have developed a thermodynamic based life

cycle assessment to provide data on precious metal recycling out of e-waste through black copper

smelting process. The novelty of the black copper smelting in this process is to utilise copper as the

collector for valuable metals, such as gold and silver.

Several studies have analysed the environmental impact of electronic waste treatment through LCA

(Niu et al., 2012, Hong et al., 2015, Biganzoli et al., 2015, Bigum et al., 2012, Xue et al., 2015, Rubin

et al., 2014, Wger et al., 2011). In spite of their scientific contributions, quantitative assessments of

the environmental loads due to recovery of precious metals out of waste PCBs are not included in the

calculation of the aforementioned studies. Inventory databases are also variable in terms of geography

and uncertainties involved, hence accurate results for Australian case studies are difficult to obtain.

On the other hand LCA involving waste electronic equipment have generally been carried out from a

product life cycle (Andrae and Andersen, 2010), including an emphasis on different waste

management alternatives (Mayers et al., 2005, Park et al., 2006). Hagelken and Meskers (2009)

assessed the savings in CO2 emissions from the recycling of metals in e-waste based on measurements

at the Umicore facility (Belgium) and saved CO2 emissions from the avoided production of metals

from virgin sources (data from Ecoinvent). The resource issues are however often related to iron;

aluminium and copper e.g. (Mayers et al., 2005, Hischier et al., 2005) and often the LCA studies have

not in any detail included the precious metals. The purpose of this study is to establish a life cycle

inventories (LCIs) for the recycling and recovery of copper, gold and silver by an LCA approach and

to evaluate the environmental impacts connected to the recovery of metals from high-grade waste

electronic equipment (WEE). High-grade WEE is the richest on precious metals containing products

from IT and telecommunications equipment such as high grade boards (green boards with gold

corners on IC chips). In this regard, this paper aims to address the above-mentioned needs in

identifying the key factors to improve e-waste treatment process in Australia, characterize and

compare the recycling methods with and without adding e-waste to the feed of a secondary coper

smelting process.

2. Process description
2.2. Pyrometallurgical route

Pyrometallurgical processes involve the use of high temperature processes to extract metals. The

typical processes include incineration, smelting in furnaces, drossing, sintering, melting and reactions

in a gaseous phase at high temperatures (Wu et al., 1993, Peters et al., 1968, Hagelken and Meskers,

2009) to process and to recover non-ferrous metals as well as precious metals from e-waste. In a

smelting process, the e-waste is injected into a high-temperature furnace and typically integrated into

a base metal production process (such as copper, lead and zinc smelter) which the base metal act as a

carrier for valuable metals such as gold, silver, platinum and palladium. For example, during copper

smelting, these valuable metals in the PCBs can be recovered and enriched into liquid copper. The

impure copper can then undergo an electro-refining process for producing high purity copper and the

precious metals are recovered from the sludge by-product through various extraction processes. An

extremely wide range of copper-bearing scraps and residues are to be found in the feed material of the

secondary copper smelter. The typical production routes employed mainly three basic grades or types

of scraps include: High-grade copper scrap (mainly of electrolytic quality which may be subjected to a

simple melting operation or pyrometallurgical refined), low-grade coppers (contaminated with

relatively small quantities of lead, tin, solder and other metallic materials), copper bearing residues,

dust, slags, mixed metals and irony copper. The secondary copper smelters raw material usually

contains copper in the metallic or oxidised form, sulphidic raw material, fluxes and additives together

with necessary reductants (e.g. coal, coke, fuel oil, and natural gas). The most common raw material

for secondary copper production is metallic raw materials (different scraps from copper and copper

alloys) and oxidic materials (copper-rich slags, ashes, drosses, dust and sludges). The process stages

used depends on the copper content of the secondary raw material, its size distribution and the other

constituents (Traulsen et al., 1982, Rentz et al., 1999). Depending on the metal content and the type of

the feed, the smelting step to produce copper metal from secondary materials may comprise several

stages such as reduction, oxidation/slagging and volatilisation. The subsequent fire refining and

electrolytic refining process are similar to the primary copper production. Depending on the purity

and composition of the copper containing materials, they are added at different stages of the process.

In this study, processing of e-waste through secondary copper smelting (black copper route) was
selected. Figure 1 presents the outline of the considered recycling route in this study. The overall

process route selected in this study is shown in Figure 1. This includes a reduction process, followed

by an oxidation. The resulting copper then can be processed through an optional fire-refining process

before further process through electro-refining to produce high purity copper or electrowinning to

recover precious metals (Ag and Au). The detailed explanation of the process and clear demonstration

of system boundaries are indicated in the next sub section.

The copper scrape and shredded waste printed circuit boards are fed into the plant in a mix FCS slag,

coal and oxygen enriched air prior to melting. The melted product called black copper is hereafter

transferred to the oxidation process. The anode refinery consists of the anode casting plant and the

electrolytic refinery. The anode casting plant deoxidizes the blister copper and cast the resulting anode

copper which is then transferred to the electrolytic refinery. The electrolytic refinery converts the

anode copper into the product copper cathodes. The conversion results in a production of anode slime

which contains gold, silver and platinum group metals (PGM) that pumped to the precious metals

refining process. The electrolytic refinery receives a flow from the precious metals refinery from

which additional copper and nickel sulphate is produced (Bigum et al., 2012). The precious metals

refinery also produces a residue from which gold, silver, palladium and Platinum Group Metal (PGM)

sludge is produced. The selected annual throughput for secondary copper smelting process and e-

waste processing plant embedded in a secondary copper smelting process is 110,000 tonnes. There are

a number of processes available to treat different secondary copper materials (Agrawal and Sahu,

2010). The overall process route selected in this study is shown in Figure 1. To evaluate the effect of

waste emission on different environmental indices of recycled materials, the e-waste processing plant

embedded in a secondary copper smelting process with total annual throughput of 110,000 tonnes has

been thermodynamically modelled and compared with secondary copper smelting process with the

same annual capacity. Secondary copper refers to all non-primary sources, such as copper containing

metallurgical wastes (low grade slags, anode slimes), industrial wastes, (copper sheeting, bars, pipes

etc) and consumer wastes (brass and bronze applications).


Fig 1 schematically view of the modelled metallurgical facility and its output

2.3. Reduction stage

The first stage of the process is a reduction in a furnace where the feed materials include copper scrap

and oxides, waste PCBs, ferrous calcium silicate (FCS) slag and coke. Some oxygen-enriched air was

also inputted to provide sufficient oxygen for the burning of coke and carbon from the PCB waste. It

has been reported in the literature that about 40 to 60% O2 enriched air is used for reduction process in

the reduction smelters (Davenport et al., 2002, Khaliq et al., 2014) . In this study, the oxygen-enriched

air composition was approximately 54% O2 and 46% N2 (Ghodrat et al., 2017). In practice, the heat

and the reducing condition are provided by the combustion of excess coke by the enriched-oxygen air

supplied in the feed materials. The equilibrium calculations for the reduction stage were carried out

for temperatures of 1100oC to 1600oC, and oxygen partial pressures (pO2) of 10-7 to 10-10 atm

(Ghodrat et al., 2016). During the reduction process, most of the impurities such as Pb, Ni, Sn, Zn, Ag

and Au were predicted to segregate in the liquid copper, although some of them were also distributed

to the slag and vapour phases (metals and oxides fumes).

2.4. Oxidation stage

In the next stage of the process, the black copper is oxidised. During this process, controlled oxidation

is exercised where oxygen-rich air is injected into the reactor and oxidise the impurities from liquid

copper and segregate them into the slag and vapour phases. Metal impurities such as Zn, Pb, Fe and
Sn are more reactive with oxygen compared to Cu, and therefore preferentially form their stable

oxides (slag). Consequently, these are removed from black copper during the oxidation process.

Precious metals such as Ag and Au are passive to oxidation and are retained in the liquid copper

during both reduction and oxidations stages. Ag and Au are recovered later in the last stage of copper

processing (Anindya et al., 2013, Rentz et al., 1999). The compositions of the black copper used for

thermodynamic modelling of oxidation process for both EWP and SCR are given in Table 1. Ferrous-

calcia-silica (FCS) flux/slag was introduced in the feed material to absorb the oxides impurities

generated during the oxidation stage to form slag. During the black copper oxidation, additional heat

(when necessary to melt fluxes) is supplied by the burning of carbon from coke or hydrocarbons, and

the oxidising condition is achieved from the excess oxygen. In the thermodynamic modelling of the

oxidation stage, pure carbon was supplied in the feed material, and oxygen was added incrementally

in multi-steps/stages. The increase in step/stage may also represent the increase in oxidation time

during the process.

Table 1 Compositions of black copper subjected to oxidation for EWP and SCR

Scenario Metal Cu Pb Sn Zn Ni Fe Br Ag Au
EWP Wt% 87.9 2.5 3.58 0.28 5.3 0.003 0.00004 0.18 0.09
SCR Wt% 84.43 7.15 4.08 0.23 4.11 0.0014 - - -

3. Methodology

In this study the mass balances of the considered recycling routes are obtained from HSC Chemistry

thermochemical package (HSC and HSC Sim 7.1&8).

The distribution of elements in the various streams (molten metal, off gas and slag) is predicted from

the equilibrium calculations carried out using FactSage 6.4 (Bale et al., 2009). FactSage is based on

an integrated databases computing system for chemical thermodynamic analysis. It has an optimized

database for the solutions such as alloys, liquids, solid oxides and slags. The Equillib module of

FactSage is used for the calculations which incorporate the Gibbs free energy minimization technique

to predict the thermodynamically stable phases under given conditions.


Two scenarios are considered: (1) recycling of precious metal out of waste PCBs through secondary

copper smelting (Electronic waste Processing, EWP); and (2) secondary copper smelting without

adding electronic waste to the feed (SCR).

Recovery rates, as well as qualities, quantities, losses and fugitive emissions for all materials and

elements used in both scenarios are calculated by HSC chemistry Sim.8. HSC chemistry

thermodynamic package is linked with GaBi environmental software (PE, 1992) and has been utilized

to show how the environmental performance of secondary copper smelting and e-waste processing

embedded in secondary copper smelting can be compared. Thermodynamic modelling of both

scenarios and calculating the environmental impact with GaBi must be done separately for e-waste

processing and secondary copper smelting without adding e-waste. The reason is mainly to assess and

justify the effect of adding electronic waste (Waste Printed Circuit Boards) on different environmental

indices.

Figure 2 indicates the detailed flowsheet developed using HSC Sim 8.0 showing the streams in each

unit process. The difference between the EWP and SCR scenarios was that the latter do not have

waste PCB/e-waste as input in Figure 2. Figure 2, shows the mass balance for recycling precious

metal out of waste printed circuit board through secondary copper smelting.

The compositions of the main feed utilised in this study are given in Table 2 to Table 5 below. These

have been given previously in the works of Khaliq et. al. (2014) and Ghodrat et. al. (2016).

The chemical identification of the composition of e-waste materials is an important step to lead to the

establishment of safe recycling procedures and final disposal of e-waste. Several researchers

investigate the composition of the electronic waste materials. For example ngel Aguirre et al.,

(2013) identified a high Cd, Ni and Pb concentrations in the particulate matter (PM), Yamane et al.,

(2011) characterized and compared the PCBs from mobile phones and computers and showed that

there are differences of metals composition (63% w/w in mobile phones and 45% w/w in computers).

To the best of our knowledge, the general perspective for electronic waste for example mobile PCBs

is, with the technological development, new materials are introduced every year in the market and to
predict e-waste elemental composition and identification of hazardous elements is not a simple task

(Tsydenova and Bengtsson, 2011, Shen and Forssberg, 2003, Hadi et al., 2015).

The results of the mass balance for each unit in the process flowsheet of the black copper smelting are

shown in Figures 3 and 4, for both the EWP (with PCB addition) and SCR (without PCB addition)

scenarios. The values shown in the input and output streams are indicating the amount of the materials

flow in tonne. As can be seen from Figure 3, for the first scenario (EWP) a total input rate of 12.5

tonnes per hour of feed materials, composed of approximately 48 wt% copper scrap/metal oxides, 48

wt% waste PCB, 3.4 wt% slag and 0.6 wt% reductant (in this study, coke was chosen as reductant)

was fed into the reduction furnace . For comparison, the second scenario (SCR) was also modeled

with the same amount of total input materials (12.5 tonnes per hour) consisted of 96 wt% copper

scrap, 3.4% wt% slag and 0.6 wt% coke as the main feed for the reduction stage.

Fig 2 A detailed flowsheet of the process selected in the study showing the streams for each

unit

Table 2 Composition of copper scrap/metal oxides used for the feed [8, 49]

Metal/Oxides Cu Cu2O SnO2 PbO ZnO NiO


wt% 70 7 5 8 5 5
Table 3 Composition of slag with ratio of FeO/SiO2 = 1.2 used for the feed [8, 49]

Flux Component FeO CaO SiO2


wt% 45 17 38

Table 4 Composition of metallurgical coke used for the feed [8, 49]

Elements C H2O S Al2O3 FeO


wt% 90 5 0.80 2 2.2

Table 5 Selected compositions of PCB used for the feed [8, 49]

Elements Cu Ag Au Al Zn Pb Fe Sn Ni Br N C Al2O3 SiO2

wt% 20 0.20 0.10 5 4 6 8.7 4 2 4 5 10 6 24


Fig 3 Mass balances for EWP (unit in tonne)

Fig 4 Mass balances for SCR scenario (unit in tonne)

4. Life cycle impact assessment

In this paper, life cycle impact assessment (LCIA) results are calculated at midpoint level by using the

ReCiPe method (Goedkoop et al., 2009) because the fate exposure of this model is consistent with

multimedia modelling. ReCiPe is a developing LCIA method attempting to combined midpoint and

endpoint impact assessment (as with IMPACT 2002+). ReCiPe 2009 comprises two sets of impact

categories with linked sets of characterisation factors. Eighteen impact categories are addressed at the

midpoint level and at the endpoint level. Most of these midpoint impact categories are further

converted and combined into three midpoint categories. The complete characterization factors and

detailed methodology for ReCiPe are obtainable on the website of Institute of Environmental Science

in Leiden University of Nederland (http://www.cml.leiden.edu/research/industrialecology/

researchprojects/finished/recipe.html). The steps that are tracked during LCA design are discussed in

the following sections.


4.1.Scope definition

The objective of this study is to establish a scientific baseline that can assess the key environmental

impacts related to recovering precious metal out of waste PCBs (through back copper route),

determine the main pollution processes and compare them with secondary copper recycling without

adding waste PCBs to the feed.

4.2.Functional unit

In this study, two scenarios were analysed and compared. For the first scenario (EWP), i.e. recycling

of precious metal out of waste PCBs through secondary copper smelting, a total input rate of 12,500

kilograms per hour of feed materials, composed of approximately 48 wt% copper scrap/metal oxides,

48 wt% waste PCB, 3.4 wt% slag and 0.6 wt% reductant (in this study, coke was chosen as reductant)

is selected as the functional unit to provide a quantified reference for all other related inputs and

outputs. All air, water, and soil emissions, raw materials and energy consumption, and waste disposal

are based on this functional unit. For the second scenario (secondary copper recycling, SCR), the

same amount of total input materials (12,500 kilograms per hour) consisted of 96 wt% copper scrap,

3.4% wt% slag and 0.6 wt% coke is defined as functional unit.

4.3.System boundary

System boundaries are set by applications by a cradle-to-gate approach. Fig. 5 represents the system

boundary for the two scenarios. The secondary copper recycling scenario (SCR) is simpler than the

EWR scenario because the pollutant of the precious metal refining is excluded in this scenario. The

EWR scenario involves raw material and energy consumption; road transportation of raw material to

the e-waste treatment site; direct air, water, and soil emissions during e-waste treatment processes

(i.e., anode refining, electro refining and precious metal refining); and waste disposal (i.e., on-site

wastewater, landfill and leachates treatment). To simplify the LCA analysis of the selected scenario,

the common process of e-waste collection is excluded. The infrastructure (i.e., construction and

equipment) process is also excluded because of the lack of information for the considered e-waste

treatment site. Hence the system boundaries include all the pyrometallurgical treatment processes,
from the moment the waste enters to the first furnace to when it leaves the system as an emission

(solid, liquid or gaseous) or as a secondary raw material or by-product. They thus included

transportation of the pre-processed waste, copper scrape, slag and coal to the treatment plant and the

subsequent incinerating treatment of all raw materials in the recycling plant as shown in Figure 5. The

geographical scope of the study is regional and the study focused on conditions and technologies for

2015. Primary data were used in the modelling of the foreground system, in particular for the mileage

for waste collection and transport.

(a)
(b)

Fig 5 System boundaries for (a) EWP scenario (b) SCR scenario

5. Results and discussions

5.1.Life cycle inventories (LCIs)

LCIs are established for both scenarios with reference to available Australian data. The data for the

main treatment facilities are based on the thermodynamic modelling of the pyrometallurgical process.

Table 6 presents the LCIs and refers to the data sources. The electricity consumption of the plant was

calculated based on thermodynamic model built in HSC Chemistry sim8. Copper scrap and electronic

waste sorted from the pre-treatment plant are via the market recycled at other plants. The

pyrometallurgical process data considered as an aggregate LCI results which exported from HSE to

GaBi.

Table 6 LCI data refer to data source

Input Output

Parameter Flow Quantity Amount Unit Parameter Flow Quantity Amount Unit Tracked flows

Electricity [electric Energy (net calorific 8 MJ Copper cathode Mass 1 kg X

power] value) (>99.99 Cu)


Energy MJ (nonspecific) Energy (net calorific 8.3 MJ Gold [Metals] Mass 0.000578 kg X

value)

Hard coal, at consumer Mass 0.0159 kg Silver [Metals] Mass 0.00113 kg X

Australia

Mass for transport Mass 1.18 Kg Electrolytic steam Mass 0.556 kg *

[Resource]

Mass for transport Mass 1.19 Kg Slag [Waste for Mass 1.31 kg *

recovery]

Mass for transport Mass 0.358 Kg Treatment residue Mass 0.009 kg *

Cargo Mass 0.2 Kg Carbon dioxide Mass 2.05 kg

Oxygen [Renewable Mass 2.37 Kg Carbon monoxide Mass 2.07 kg

resource]

Sulphuric acid (96%) Mass 0.561 Kg Dust (>PM10) Mass 2.89 kg

Methane Mass 0.159 Kg Heavy metals to air Mass 0.148 kg

Air Mass 1.89 Kg Sulphur dioxide Mass 0.000104 kg

Water vapour Mass 0.215 kg

The recovery of metals at the metallurgic plants cause loss of metal to dust ejects etc. The recovery

rates for the metallurgic processing were calculated based on GaBi version 13 and presented in Table

7 together with original content of the material and resources in the considered scenarios.

Table 7 LCI data for the pyrometallurgical plant used in this study

Pyrometallurgical plant (per 1 kg out-coming Cu)

Description Value Value Unit

EWP SCR

Energy 2.0 0.55 kWh

Electricity

Material and resource 4.01103 1.89103 Kg


Emission to air 66 24.3 kg

Heavy metal to air 0.148 0.00985 kg

Inorganic emission to air 39.3 17.5 kg

Organic emission to air group (VOC) 0.00955 0.00351 kg

Other emission to air 23.7 6.57 kg

Particle to air 2.9 0.241 kg

Pesticide to air 1.5410-8 7.510-9 kg

Radioactive emission to air 5.4210-14 2.6810-14 kg

Emission to fresh water 3.91103 1.85103 kg

Emission to sea water 17.4 6.25 kg

Emission to agricultural soil 1.7510-6 1.5810-6 kg

Emission to industrial soil 1.3510-5 1.3310-6 kg

Operational data (i.e., energy, chemicals, raw material, water and wastewater, solid waste, and

product) and direct emissions to water, air and soil associated with the considered scenarios are also

calculated to generate a LCI. Table 8 gives representative information regarding these emissions for

EWP and SCR scenarios.

Table 8 LCI data for direct emissions

Unit EWP SCR


Amount Amount
Emission to air
Heavy metals to air Kg 0.148 0.00985
-8
Antimony kg 4.2210 1.4410-8
Arsenic kg 4.1810-7 1.310-7
Cadmium kg 6.2410-7 6.4510-9
Chromium kg 5.4810-7 1.8210-7
Cobalt kg 2.2210-7 6.6210-8
Lead kg 7.5910-7 5.4710-7
Mercury kg 2.89e-5 4.5510-8
Selenium kg 6.5510-7 2.8810-7
Silver kg 1.4810-8 7.3410-9
Zinc kg 1.6610-6 5.8810-8
Tin kg 3.6810-7 1.210-7
Heavy metal to air kg 0.148 0.00984
(unspecified)
Inorganic emission to air Carbone dioxide kg 7.63 3.93
Carbon dioxide (biotic) kg 0.255 0.0121
Carbon monoxide kg 2.07 0.0095
Nitrogen oxide kg 0.011 0.00294
Nitrogen monoxide kg 0.00174 0.000844
Sulphur dioxide kg 0.0117 0.00539
Water (evapotranspiration) kg 9.42 5.71
Water vapour kg 21.5 7.45
Organic emission to air (group VOC) Kg 0.00993 0.00336
Group NMVOC to air Kg 0.000982 0.000447
Methane Kg 0.00882 0.00291
Other emission to air Exhaust Kg 18 6.31
Particles to air
Dust (>PM10) Kg 2.89 0.00019
Dust (PM2.5-10) Kg 0.000842 0.238
Dust (PM 2.5) Kg 0.00444 0.00211
Emission to fresh water
Heavy metal to fresh water Iron Kg 0.00234 0.00085
Inorganic emission to fresh water
Chlorine /chloride Kg 0.00439 0.0242
Calcium Kg 0.00139 0.000511
Nitrite kg 0.000336 0.00037
Sodium kg 0.00475 0.00211
Sulphate Kg 0.00706 0.00282
Organic emission to Fresh water
Carbon organically bound Kg 0.00053 0.00036
Particle to fresh water
Soil loss by erosion into water Kg 0.00519 0.00326
Soil suspended kg 0.0022 0.000832

5.2.Life Cycle Impact assessment (LCIA)

LCIA aims to evaluate the significance of potential environmental impacts using the results coming

out from the LCI phase. Table 9 presents the LCIA midpoint assessment results with the use of the

ReCiPe method. The EWP scenario has a high potential impact on human health, photochemical

oxidant formation, Terrestrial acidification, water depletion, metal and fossil depletion. Coal-based
electricity generation and the distance the material feed travels are significantly contributed to the

overall environmental burden for both scenarios.

Landfill disposal showed an additional dominant contribution to the overall environmental burden for

the SCR scenario, whereas the additional dominant process for the EWP scenario showed direct

pollutant emissions as a result of untreated metal oxide dust ejected to the environment.

Table 9 LCIA midpoint assessment results by using the ReCiPe method.

Category Unit EWP SCR


Amount Process Amount Process
Climate change kg CO2 eq 7.9 Electricity (28.4%) + main pyro 4.05 Main secondary copper
and refining process for e-waste smelting process (58.1 %)
treatment (26.1%) +Slag (22.8%)
+electricity (13.94%)
Ozone depletion kgCFC-11 1.5510-10 Slag PE (93.46%) 7.9710 Slag PE (94.2%)
-11
eq
Human toxicity kg1,4-DB 15.3 Sludge acid/basic PE (98%) 0.204 Waste water treatment
eq (60%)+ electricity (19.5%)
Photochemical oxidant kg NMVOC 0.107 Main pyro and refining process 4.2810 Electricity (40%) + slag
-3
formation for e-waste treatment (88%) (31.25%)
Particulate matter formation kg PM10 eq 0.0101 Slag PE (54.28%) +Electricity 4.3910 Slag PE (66.4%) +Electricity
-3
(33%) (18.6%)
Ionising radiation kg U235 eq 0.169 Slag (95.8%) 0.0861 Slag (97.3%)
Terrestrial acidification kg SO2 eq 0.0181 Electricity (50%) + Slag (20%) 7.2510 Sulphuric acid (37.86%)
-3
+Sulphuric acid (17%) +Electricity (31.75%)
-5
Freshwater eutrophication kg P eq 3.210 Waste water treatment (75.6%) 2.8610 Waste water treatment
-5
+ Slag PE (2.03%) (84.45%)
Marine eutrophication kg N eq 4.6710-3 Electricity (51.5%) + sludge 1.4810 Electricity (41.38%) + Slag
-3
(acid basic) 20% + Slag PE (31.66%)
(19%)
Terrestrial ecotoxicity kg 1,4-DB 3.0810-3 Sludge (96.1%) 7.1410 Waste water treatment
-5
eq (48.988%) + Slag (28.32%)
Freshwater ecotoxicity kg 1,4-DB 4.110-3 Waste water treatment (76.8%) 3.5910 Waste water treatment
-3
eq + Slag (17.56%) (87.88%)
Marine ecotoxicity kg 1,4-DB 1.3510-3 Waste water treatment 1.1910 Waste water treatment
-3
eq (76.11%) + (86.44%)
Water depletion m3 3.99 Slag PE (84%) 1.87 Slag (92.4%)
Metal depletion kg Fe eq 0.0122 Slag PE (78.1%) 0.0186 Sludge (74%)
Fossil depletion kg oil eq 1.86 Electricity (35.2%) + Slag PE 0.0708 Slag (38.18%)+ Electricity
(27.82%) (23.34%)+ Sulphuric acid
(20%)
Fig 6 LCIA results for EWP and SCR scenarios

Figure 6 shows the LCIA results for EWP and SCR scenarios. The results indicate that almost all

environmental impacts for SCR scenario is lower than the one in EWP scenario. This is mainly

because further processing of metal oxides dusts needed to be conducted for the EWP scenario.
70

EWR SCR
60

50

40
Mass (kg)

30

20

10

0
Emission to air Emission to fresh Emission to sea Emission to Emission to Resource
water water industrial soil agricultural soil depletion

Fig 7 ReCiPe endpoint analyses from GaBi for EWP and SCR scenarios

5.3.Contribution of substance to the key categories

For both scenarios, the most dominant substances that contribute to climate change are carbon dioxide

and methane. The emissions of heavy metal dust such as arsenic, selenium and lead to air and arsenic,

selenium and mercury to water have major effect on human toxicity. The foremost substance in

photochemical oxidant formation and Terrestrial acidification is nitrogen oxide. The emissions of

non-methane volatile organic compounds to air and nitrate and ammonium to water are additional

dominant substances in photochemical oxidant formation and marine eutrophication respectively. In

particulate matter formation and terrestrial acidification, nitrogen oxides and sulphur dioxide emitted

to the air are the most significant substances. The particulate emission also plays a key role in

particulate matter formation. Phosphate and heavy metals in water have a dominant contribution to

freshwater eutrophication. vanadium, nickel, selenium , beryllium are the most significant substances

in freshwater ecotocxicity. The emission of bromine to water has an additional main contribution to

freshwater ecotoxicity. The use of coal, natural gas, and oil also significantly contributes to fossil
depletion. In addition, the substances that contributed the most to each dominant category are lead,

zinc and nickel to soil from the solid waste open dumping stage for both scenarios. Direct copper

from the waste open dumping process also contribute an important role in most categories, except for

human toxicity. Ammonia , nitric acid and chloride came from inorganic emission to industrial soil

are additional dominant substances in most categories, except for terrestrial ecotoxicity. Direct barium

and antimony emissions from the same process are additional dominant substances in most categories,

except for terrestrial ecotoxicity.

5.3.1. Discussion

Although the LCA of e-waste has been extensively studied (Song et al., 2012; Niu et al., 2012), the

potential environmental impact of e-waste treatment widely varies (Kiddee et al., 2013) for example

Hong et al. (2009) compared incineration and melting technologies, which are methods of waste

disposal by burning at 800900 o C and 13001800 o C, respectively. Their results showed that waste

melting technology can significantly reduce toxic pollutants because of their crystallizability at high

temperature. Based on Hong latest study, (Hong et al., 2015) the overall environmental impact of the

e-waste treatment with end-life disposal scenario and incineration scenarios is mainly attributed to

human toxicity, freshwater ecotoxicity, and marine ecotoxicity. Their research showed that the impact

of freshwater eutrophication and terrestrial ecotoxicity also plays an important role in the e-waste

treatment with end-life disposal and incineration scenarios, respectively. In this study we have shown

the impact of EWP (recycling of precious metal out of waste PCBs through secondary copper

smelting) scenario on the climate change, freshwater eutrophication and fossil depletion is

significantly higher than those obtained from the secondary copper recycling without adding

electronic waste to the feed (SCR) scenario, this is aligned with what previous studies reported. For

example Niu et al. (2012) proved that e-waste incineration can generate a significant environmental

burden compared with other kinds of incineration because of the direct toxic material emissions. Song

et al. (2012) studied e-waste incineration technologies by using Eco-indicator 99 method on the

basis of the Ecoinvent database and showed that the overall environmental impact from the

incineration scenario is approximately 37 times higher than that from landfill. The difference in
overall environmental burden between different studies is mainly because of regionalization,

uncertainties, and geographical variability in the applied inventories and LCIA models. The energy

type and system boundaries considered in each research also played additional roles in this variation.

5.4.Sensitivity analysis

The key sensitivities in this study are the electricity mix to which the smelter is coupled and the

distance which the scrap is transported from its origin. To demonstrate the methodology through this

study, it is assumed that the electricity mix to which the smelter is coupled is the same as that for the

overall region in which the smelter is located. The EWP scenario takes the case of printed circuit

board being available in New South Wales region for recycling to produce copper, silver and gold.

The question to be answered is whether the scrap collected in the major Australian cities should be

trucked to existing smelter in Victoria or shipped to Southeast Asia (China) for recycling in available

reverberatory furnace. The environmental performance is again based on LCA and input-output

models and can be used to allow more informed strategic decision making. The sensitivity of the

environmental performance to transport consideration used in each location is hard to obtain, instead,

the study only demonstrates sensitivities in environmental performance to electricity source.

Given the major contribution that the power consumption of the various pyrometallurgical processes

makes to the total environmental impact the whole process, and the difficulties encountered in

establishing the various base case values, a sensitivity analysis was carried out by varying the process

power consumptions (electricity) by 10% below the base case values. Table 10 shows the sensitivity

analysis results obtained from the study. A 10% decrease in electricity consumption obtains

approximately 0.23 kg CO2 eq, 0.07 kg oil eq, 0.04 m3, 0.01 kg P eq and 0.01 kg 1, 4-DB eq

environmental benefit in climate change, fossil depletion, water depletion, Freshwater eutrophication

and marine ecotoxicity respectively. For the rest categories and processes, a similar analogy can be

made with the sensitivity results shown in Table 10. As can be seen from data given in Table 10, for

EWP scenario, cut in electricity consumption has the higher environmental benefit in all dominant

categories, except human toxicity, terrestrial eco-toxicity and photochemical oxidant formation. For

SCR scenario on the other hand, 10% reduction in electricity consumption has the lowest
environmental benefit on three categories: freshwater eutrophication, freshwater eco-toxicity and

metal depletion. Climate change yet produces the highest variability.

Table 10 Sensitivity of main contributors, values are presented per functional unit

Electricity decrease Scenarios


EWP SCR
Variation 10% 10% 10%
Climate change (kg CO2 eq) 0.23 0.06
Human toxicity (kg1,4-DB eq) 0 0.003
Freshwater eutrophication (kg P eq) 0.01 0
Water depletion (m3) 0.04 0.01
Marine ecotoxicity (kg 1,4-DB eq) 0.01 0.0110-3
Terrestrial acidification (kg SO2 eq) 0.0009 0.2210-3
Particulate matter formation (kg PM10 eq) 0.00034 0.0810-3
Metal depletion (kg Fe eq) 0.0002 0
Fossil depletion (kg oil eq) 0.07 0.017
Freshwater ecotoxicity (kg 1,4-DB eq) 0.0110-3 0
-3
Marine eutrophication (kg N eq) 0.2410 0.0610-3
Photochemical oxidant formation (kg NMVOC) 0 0.1710-3
Terrestrial ecotoxicity (kg 1,4-DB eq) 0 0.1210-5

6. Conclusion

This paper analysed the LCIA of the recovery of copper and other valuable metals from waste printed

circuit board (PCBs) through a base metal secondary pyrometallurgical operation and compared the

results with general secondary copper recycling without adding e-waste to the feed.

Two scenarios have been considered namely, EWP (copper recycling with PCB waste addition) and

SCR (general copper recycling). The study supported by rigorous thermodynamic modelling using

HSC Chemistry 8.0 and FactSage 6.4 thermodynamic packages. HSC Chemistry 8.0 is linked with

GaBi environmental software and was utilized to show how the environmental performance of the

two scenarios can be compared.

The key findings of this article showed that the impact of the EWP scenario for climate change,

freshwater eutrophication and fossil depletion are significantly higher than those obtained from the

SCR scenario, this is mainly because the metal and oxide dust in EWP scenario needs to be further
refined which is out of the scope of this article. A further investigation on this topic is therefore

required.

A sensitivity analysis was also conducted by varying the process power consumption. It has been

concluded that in EWP scenario, a 10% cut in electricity consumption has the higher environmental

benefit in all dominant categories, except human toxicity, terrestrial eco-toxicity and photochemical

oxidant formation. For SCR scenario on the other hand, 10% reduction in electricity consumption has

the lowest environmental benefit on three categories: freshwater eutrophication, freshwater eco-

toxicity and metal depletion. Climate change yet produces the highest variability.

It could also be concluded that the overall environmental impact of the EWP scenario might be lower

than what has been calculated in this study considering the environmental burden of producing metals

and precious metals from virgin source. The adequate setting of recycling plants requires gathering

and analysis of information on several aspects of material recovery in order to help not only the

design, but also the operation and maintenance of such systems in Australia and in the absence of a

consolidated structure; the most basic choices are yet to be made. In this sense, this study can shed

light on e-waste treatment embedded in existing secondary copper recycling facilities as an effective

alternative for e-waste management, while the comparison between the two introduced scenarios

demonstrated the importance of LCA as a useful tool in decision making.

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