Department of Process Engineering

Mineral Processing 415

E-waste recycling during secondary copper smelting operation

K Raju
23736941

20 April 2023
© Stellenbosch University
2
Plagiarism Declaration

I, Kyle Raju (23736941), declare that:

 I have read and understand the Stellenbosch University Policy on Plagiarism and the
definitions of plagiarism and self-plagiarism contained in the Policy [Plagiarism: The use of
the ideas or material of others without acknowledgement, or the re-use of one’s own
previously evaluated or published material without acknowledgement or indication thereof
(self-plagiarism or text recycling)].
 I also understand that direct translations are plagiarism, unless accompanied by an
appropriate acknowledgement of the source. I also know that verbatim copy that has not
been explicitly indicated as such, is plagiarism.
 I know that plagiarism is a punishable offence and may be referred to the University's
Central Disciplinary Committee (CDC) who has the authority to expel me for such an offence.
 I know that plagiarism is harmful for the academic environment and that it has a negative
impact on any profession.
 Accordingly all quotations and contributions from any source whatsoever (including the
internet) have been cited fully (acknowledged); further, all verbatim copies have been
expressly indicated as such (e.g. through quotation marks) and the sources are cited fully.
 Except where a source has been cited, the work contained in this assignment is my own
work and that I have not previously (in its entirety or in part) submitted it for grading in this
module/assignment or another module/assignment.

20 April 2023

Signed Date

3
Abstract

This report presents a detailed thermodynamic analysis, flowsheets, mass, and energy balance
analysis of the secondary copper recycling process for electronic waste, specifically printed circuit
boards (PCBs). Two scenarios were compared: secondary copper recycling with and without the
addition of PCBs. During scenario one, the thermodynamic analysis predicted that a temperature of
1300°C and an oxygen partial pressure (pO2) of 10 -12 atm are suitable for processing PCBs through
secondary copper smelting. The predicted wt% of copper (Cu), gold (Au), and Cu 2O and CO2 from
scenario one was 82.92 wt%, 0.086wt%, 0.121 wt%, and 5.21 wt% respectively. The copper recovery
was found to be 99.86%. During scenario 2, the thermodynamic analysis predicted that a
temperature of 1300°C and an oxygen partial pressure (pO2) of 10 -11 atm are suitable for processing
PCBs through secondary copper smelting. The predicted wt% of copper (Cu), and Cu 2O and CO2 from
scenario two was 84.17 wt%, 0.25 wt% and 19.95 wt% respectively. The copper recovery was found
to be 99.99%.

Overall, this report provides insights into the secondary copper recycling process for e-waste,
highlighting the importance of optimizing processing conditions to maximize metal recovery and
minimize environmental impact.

4
Table of Contents

Plagiarism Declaration...........................................................................................................................2

Abstract.................................................................................................................................................3

Table of Contents..................................................................................................................................4

1 Introduction...................................................................................................................................5

2 Process Conceptualisation.............................................................................................................5

2.1 Process Description................................................................................................................5

2.2 Inlet Stream Information.......................................................................................................6

3 Thermodynamic Modelling Methodology.....................................................................................6

4 Results and Discussion...................................................................................................................7

4.1 Mass Balance.........................................................................................................................7

4.1.1 Scenario 1......................................................................................................................7

4.1.1.1 Reduction...................................................................................................................7

4.1.1.2 Oxidation..................................................................................................................11

4.1.1.3 Mass Balance Schematic..........................................................................................14

4.1.2 Scenario 2....................................................................................................................15

4.1.2.1 Reduction.................................................................................................................15

4.1.2.2 Oxidation..................................................................................................................18

4.1.2.3 Mass Balance Schematic..........................................................................................21

4.2 Energy Balance.....................................................................................................................22

4.2.1 Scenario 1....................................................................................................................22

4.2.1.1 Reduction.................................................................................................................22

4.2.1.2 Oxidation..................................................................................................................22

4.2.2 Scenario 2....................................................................................................................22

4.2.2.1 Reduction.................................................................................................................22

4.2.2.2 Oxidation..................................................................................................................23

4.3 Flowsheet............................................................................................................................23

5 Conclusion...................................................................................................................................24

6 References...................................................................................................................................24

Appendix A. Inlet Stream Compositions...........................................................................................25

5
1 Introduction

The issue of electronic waste has become a significant environmental and health concern due to the
hazardous substances that can be present in discarded electrical and electronic equipment.
However, e-waste can also be a valuable resource due to the high concentration of precious metals,
including gold, silver, palladium, platinum, and base metals such as copper. Printed circuit boards
(PCBs) are a specific type of e-waste that contain a significant amount of precious and base metals.
The concentration of these metals varies between different types of PCBs. The extraction of these
metals from e-waste is an economically important process, and there is growing interest in
developing recycling technologies to recover these resources. Secondary copper smelting,
specifically black copper smelting, is a versatile route for recycling PCBs, and this study aims to
develop a mass balance flowsheet supported by thermodynamic modelling carried out via FactSage
to predict the optimum temperature and oxygen partial pressure for processing PCBs through this
route as well as the requirements listed below. The process is then compared to the extraction of
base metals with the exclusion of PCBs.

Requirements:

1. Cu in the melt should not be less than 80 Wt%

2. Copper recovery should be optimum
3. Cu2O losses should be kept below 1.5 Wt%
4. Au in the melt must be as high as possible
5. CO2 in the gas phase should be kept as low as possible

2 Process Conceptualisation

2.1 Process Description

Copper smelting involves two distinct routes for treating secondary materials, one being the primary
route and the other being the black copper route. The black copper route is a significant method
used in e-waste recycling and aims to utilize waste streams from industrial recyclables without major
sulphur content. The feed to the black copper route typically includes low-grade copper scrap and
waste materials from sources like automobile shredder products, copper smelting and alloying
facilities, copper electroplating operations, and printed circuit boards (PCBs).

The flowsheets that are suitable for treating these materials aim to produce a discardable slag from
the reductive smelting step that does not need further processing. The first step involves reduction
to produce crude copper, which may contain copper, lead, zinc, nickel, and iron. A typical black

6
copper slag contains FeO, CaO, Al2O3, and SiO2. The off-gas collects fumes and dust, which is then
cooled and filtered to recover dust containing species like copper, lead, and zinc.

After crude copper treatment, oxidation of elements less noble than copper occurs in a converter to
form raw copper. Impurities are removed during the oxidation of black copper by turning them into
oxides, which are then removed to the slag phase. The resulting copper is then cast to form anode
copper. To produce high-purity cathode copper, an electrolytic refining process is utilized (Maryam
Ghodrat, 2017). Valuable metals, such as gold, are separated into anode slime during the electrolytic
refining process, which can then be recovered through hydrometallurgy or electrometallurgy
processes.

The overall black copper smelting route flowsheet can be seen in section 4.3 below.

2.2 Inlet Stream Information

This report considers 2 scenarios: The first scenario had a total feed rate of 12.5 t/h with weighted
compositions of 48% copper scrap, 48% PCB, 3.4% slag and 0.6% coke, all being fed into the
reduction stage. The second scenario had a total feed rate of 12.5 t/h with weighted compositions of
96% copper scrap, 3.4% slag and 0.6% coke, all being fed into the reduction stage. Table 1, Table 2,
Table 3 and Table 4 in Appendix A list the weighted compositions of the all the above-mentioned
feed streams. All feed input was assumed to enter at a temperature of 25C and enriched air with an
O2 wt% of 54% was used to provide sufficient oxygen to combust the coke and carbon from the
PCBs. Scenario 2 required no oxygen input for the reduction stage (Maryam Ghodrat, 2017).

3 Thermodynamic Modelling Methodology

This study employs chemical thermodynamic modelling using FactSage to assess and characterize
material and energy flows during black copper smelting of copper scrap and waste PCBs. Table 1,
Table 2, Table 3 and Table 4 list the elements included in the model, but the analysis mainly focuses
on the behaviour of Cu, Au, CO2, and Cu2O. Two scenarios were compared: scenario 1 included
waste PCBs as an input, while scenario 2 did not. The FactSage engine was used to model complex
equilibrium reactions and determine the detailed distribution of elements and phases in each unit
operation. The phase and chemical equilibria for each stage were predicted using the "Equilib"
module of FactSage, which employs the Gibbs free energy minimization technique to predict the
equilibrium of multicomponent and multiphase systems at various processing conditions (Maryam
Ghodrat, 2017). Thermodynamic databases for Cu-rich multicomponent systems and associated
slags, including FactPS, FToxide, and FTMisc, were utilized in this study (Maryam Ghodrat, 2017).

The reduction stage was modelled using Cu scrap, PCB/e-waste (scenario 1 only), slag, coke, and air
inputs, with compositions listed in Table 1, Table 2, Table 3 and Table 4. Equilibrium calculations
were conducted at temperatures between 1100 and 1600 °C and oxygen partial pressures ranging
from 10−6 to 10−12 atm, reflecting the different reducing conditions. The partial pressure cannot be

7
fixed but is rather controlled through the level of coke in the feed. For modelling purposes, the
difference in partial pressure was set manually, and the corresponding amount of air was
determined through an iterative mass balance calculation via FactSage. The output of the reduction
stage was composed of liquid Cu-rich, slag, and gas phases.

The oxidation stage was modelled at temperatures ranging from 1100 to 1600 °C and conducted
through multi-step equilibrium calculations by incrementally adding 1 tonne of oxygen. This allowed
for tracking slag formation, increasing liquid copper purity, and determining the copper deportment
to the slag as the process progressed. The output of the oxidation stage requires further processing
and can be done using fire-refining followed by electrolytic refining. However, further processing
was not analyzed in this report.

4 Results and Discussion

4.1 Mass Balance

The results of the mass balance for each unit in the process flowsheet of the black copper smelting is
shown in Figure 16, Figure 17, Figure 30 and Figure 31 for both scenario 1 and 2. The values shown in
the input and output streams are indicating the amount of the materials flow in tonne.

4.1.1 Scenario 1
4.1.1.1 Reduction
The first stage in the process was feed into the furnace for reduction with feed conditions as
mentioned in section 2.2 and unit simulation conditions as mentioned in section 3 above. The
following outputs were obtained from FactSage that fulfil the requirements mentioned in section 1
of this report.

The equilibrium concentration of copper in the liquid black copper at various oxygen partial
pressures and varying temperatures were plotted as shown in Figure 1 below, The wt% of copper
decreases from 90% to 80 % with increasing temperature from 1100 to 1600C for all isobars that
were plotted. At any given temperature, a decrease in the partial pressure of oxygen results in a
decrease of the copper wt% in the melt. Given that the copper requirement is to stay above 80%, a
partial pressure of 10-12 atm seems feasible at a temperature of 1300C since higher temperatures
and pressures will require a higher energy input into the process which in affect increases
operational costs. This process condition of 1300C and 10 -12 atm of oxygen produces a melt with
approximately 82 wt% of copper. Lower temperatures could be used to produce higher wt% of
copper in the melt and would utilise a lower amount of energy as a result.

8
 98

93
wt% cu

88

83

78
1100 1150 1200 1250 1300 1350 1400 1450 1500 1550 1600

Temperature (C)

po2=10e-12 po2=10e-11 po2=10e-10 po2=10e-9

po2=10e-8 po2=10e-7 po2=10e-6

Figure 1: Copper wt% in melt as a function of temperature at different partial pressures of oxygen

However, as can be seen in Figure 2 below. Temperatures lower than 1300C tend to produce a
higher quantity of Cu2O, which is undesirable as this represent a high copper loss into the slag phase
as Cu2O. The requirement for Cu2O is constraint to be lower than 1.5 wt%, using this constraint, a
partial pressure if 10-12 at a temperature of 1300C also seems feasible as it produces a considerably
low amount of Cu2O which is a highly desirable condition, ensuring low copper losses into the slag
phase as Cu2O. The lowest partial pressure is chosen as increasing the partial pressure of oxygen
increases the copper losses into the slag phase as Cu 2O. Lower partial pressures of oxygen also
reduce operational costs.

18.5
16.5
14.5
12.5
10.5
Another
w% Cu2O

8.5
6.5
4.5
2.5
0.5
1100 1150 1200 1250 1300 1350 1400 1450 1500 1550 1600
-1.5
Temperature (C)

po2=10e-12 po2=10e-11 po2=10e-10 po2=10e-9

po2=10e-8 po2=10e-7 po2=10e-6

Figure 2: Cu2O losses as a function of temperature at varying oxygen partial pressures

requirement is the production of the lowest possible amount of carbon dioxide as this ensures
minimal environmental impact from the process. As can be seen from Figure 3 below, the wt% of

9
carbon dioxide in the gaseous phase tends to decrease at higher temperatures and decreases as the
partial pressure of oxygen decreases. A reasonably low amount of carbon dioxide is produced at a
temperature of 1300C, relative to lower temperatures. At an oxygen partial pressure of 10 -12 the
lowest amount of carbon dioxide is produced and therefore, a temperature of 1300C and oxygen
partial pressure of 10-12 is a feasible operating point.

70

60

50

40
wt% CO2

30

20

10

0
1100 1150 1200 1250 1300 1350 1400 1450 1500 1550 1600

Temperature (C)

po2=10e-12 po2=10e-11 po2=10e-10 po2=10e-9

po2=10e-8 po2=10e-7 po2=10e-6

Figure 3: wt% carbon dioxide as a function of temperature at varying oxygen partial pressures

As
can be seen in Figure 4 below the recovery of copper increases with an increase in temperature from
1100C to 1600C for all partial pressures of oxygen.

98

93
Recovery Cu

88

83

78
1000 1100 1200 1300 1400 1500 1600 1700
Temperature (C)

po2=10e-12 po2=10e-11 po2=10e-10 po2=10e-9

po2=10e-8 po2=10e-7 po2=10e-6

Figure 4: Copper recovery as a function temperature at varying partial pressures of

oxygen

10
However, due to the above-mentioned constraints on Cu 2O losses, Cu wt% in the melt and CO2
production limits, oxygen partial pressures in the range of 10 -10 – 10-12 were evaluated for the copper
recovery as shown in Figure 5 below. All copper recoveries were above 98% at these partial
pressures of oxygen, however, it was found to decrease at temperatures higher than 1300C. The
highest copper recovery can be found at a temperature of 1300C and an oxygen partial pressure of
10-12.
100

99.5

99
Recovery Cu

98.5

98

97.5
1100 1150 1200 1250 1300 1350 1400 1450 1500 1550 1600
Temperature (C)

po2=10e-12 po2=10e-11 po2=10e-10 po2=10e-9

Figure 5: Copper recovery as a function of temperature at chosen partial

pressures.
The final
requirement of this report was the focus on maximising the amount of extracted gold. The maximum
amount of gold is found to be extracted at lower temperatures and decreases as the temperature
increases as well as with a decrease in the partial pressure of oxygen as can be seen in Figure 6
below.
0.14

0.13

0.12
wt% Au

0.11

0.1

0.09

0.08
1100 1150 1200 1250 1300 1350 1400 1450 1500 1550 1600
Temperature (C)

po2=10e-12 po2=10e-11 po2=10e-10 po2=10e-9

po2=10e-8 po2=10e-7 po2=10e-6

Figure 6: wt% gold as a function of temperature as varyign partial pressures of oxygen

11
However, given temperature constraints in meeting previous requirements, the only feasible
temperatures are those higher than 1300C. Therefore, since at higher temperatures the amount of
gold decreases the optimum temperature would be 1300C. At the constraint partial pressure from
meeting previous requirements, the amount of gold extracted is the lowest, however, the primary
importance of this process is the extraction of copper and therefore it will take precedence. The
extracted amount of gold at 1300C and a partial pressure of 10 -12 is found to be 0.09wt%. increasing
the extracted mount of gold by increasing the partial pressure would result in a lower amount of
copper recovery, higher amounts of Cu 2O losses and an increase in carbon dioxide emissions.
Therefore, a partial pressure of 10-12 is chosen.

4.1.1.2 Oxidation
In the following stage of the copper processing, black copper undergoes an oxidation process. This
involves the introduction of oxygen-rich air into the reactor, resulting in controlled oxidation. The
aim is to oxidize the impurities present in the liquid copper and segregate them into the slag and
vapor phases. During the oxidation process, metal impurities, such as Zn, Fe, Ni, and Pb, are more
reactive with oxygen than copper and, therefore, form stable oxides and are removed from black
copper (Maryam Ghodrat, 2017). However, precious metals, such as Au, do not react with oxygen
and remain in the liquid copper throughout both reduction and oxidation stages (Maryam Ghodrat,
2017). The recovery of Au takes place in the final stage of the copper processing further downstream
which is not investigated in this report.

The following outputs were obtained from FactSage under unit simulation conditions as mentioned
in section 3 above. As shown in Figure 7 below the wt% of copper in the black copper mixture
linearly increases with an increase in oxidation stage followed by a sharp decline after stage 7 of
oxidation, this trend is seen for all operational temperatures of the oxidation unit.
100

90

80

70

60
Wt% Cu

50

40

30

20

10

0
1 2 3 4 5 6 7 8 9 10
Oxidation stage

T=1100 T=1200 T=1300 T=1400 T=1500 T=1600

Figure 7: wt% copper after oxidation

The
highest wt% of copper is found at oxidation stage 7 at a temperature of 1600C, however, as seen in

12
Figure 9 and Figure 8, the highest amount of Cu 2O losses is also found at this point along with the
lowest wt% of gold. Therefore, an operational temperature of around 1300C at an oxidation stage of
3 is more feasible with copper wt% of approximately 84% and CU 2O losses around 0.003%.
100 90

90 80
80 70
70
60
60
50

Wt% Cu2O
50
Wt% Au

40
40
30
30
20 20

10 10

0 0
1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10

Oxidation stage Oxidation stage

T=1100 T=1200 T=1300 T=1400 T=1500 T=1600 T=1100 T=1200 T=1300 T=1400 T=1500 T=1600

Figure 8: wt% Au after oxidation Figure 9: wt% Cu2O after oxidation

As can be seen by Figure 10, the wt% of carbon dioxide at this operational point is also found to be
0.05%, therefore this is a highly desirable operational point.

120

100

80
Wt% Co2

60

40

20

0
1 2 3 4 5 6 7 8 9 10
Oxidation stage

T=1100 T=1200 T=1300 T=1400 T=1500 T=1600

Figure 10: wt% CO2 after oxidation

In terms of the impurities, it can be seen from Figure 11, Figure 12, Figure 13, Figure 14, Figure 15
that it is possible to completely remove impurities, however, this can only be carried out at oxidation
stages above 7, which results in a high loss of copper to the slag phase and produces a high amount
of carbon dioxide, which is undesirable. Therefore, the impurities are partially removed at an
oxidation stage of 3 with a temperature of 1300C. As can be seen in Figure 11, the wt% of of Pb in
black copper drops from 8% to approximately 7%.

13
 9

5
Wt% Pb

0
1 2 3 4 5 6 7 8 9 10

Oxidation stage

T=1100 T=1200 T=1300 T=1400 T=1500 T=1600

Figure 11: wt% Pb after oxidation

Figure 12 and Figure 13 below shows that the wt% of Zn in the black copper drops from 1.7% to 0.5%
and the wt% of S in the black copper drops from 0.00076% to 0.0006%.

2 0.0009

1.8 0.0008
1.6 0.0007
1.4
0.0006
1.2
0.0005
1
Wt% Zn

Wt% S

0.0004
0.8
0.0003
0.6

0.4 0.0002

0.2 0.0001

0 0
1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10

Oxidation stage Oxidation stage

T=1100 T=1200 T=1300 T=1400 T=1500 T=1600 T=1100 T=1200 T=1300 T=1400 T=1500 T=1600

Figure 12: wt% Zn after oxidation Figure 13: wt% S after oxidation
Figure 14 and Figure 15 below show an increase in the wt% of Ni and Fe in the black copper. This
suggest that these species have a lower preference for being oxidised. The wt% of Fe increases from
4.16% to 4.28% whilst the wt% of Ni increases from 4.04% to 4.16%. these increases are not large
and therefore an operational point of 1300C at an oxidation stage of 3 is feasible. The increases in
these wt% might not suggest that these species are increasing in amount within the black copper but
rather the purity of the black copper increasing which in effect increases the wt% of impurities. The
amount of these impurities remains the same.

14
 5 5

4.5 4.5

4 4.1.1.34
3.5 3.5

3 3

2.5 2.5

Wt% Fe
Wt% Ni

2 2

1.5 1.5

1 1

0.5 0.5

0 0
1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10

Oxidation stage Oxidation stage

T=1100 T=1200 T=1300 T=1400 T=1500 T=1600 T=1100 T=1200 T=1300 T=1400 T=1500 T=1600

Figure 15: wt% Ni after oxidation Figure 14: wt% Fe after oxidation

Mass Balance Schematic

Considering sections 4.1.1.1, the optimum conditions for the reduction unit was chosen to be 1300C
with a partial pressure of oxygen as 10 -12 atm, A mass balance shown below is done at this operating
condition.

Figure 16 below shows the mass balance on the reduction unit for scenario 1 with inlet conditions as
mentioned in section 2.2 and thermodynamic methodology mentioned in section 3.

6 t/h PCB 0.37 t/h metal oxide

6 t/h scrap 6.95 t/h black copper

0.425 t/h slag 3.76 t/h exhaust gas

Reduction
0.075 t/h 3.17 t/h slag
coke
1.96 t/h Air 0.21 t/h Solid spinel oxide

Figure 16: Mass balance on reduction unit

15
 Considering section 4.1.1.2, the optimum conditions for the oxidation unit was chosen to be 1300C
at stage 3 oxidation, A mass balance shown below is done at this operating condition.

Figure 17 below shows the mass balance on the oxidation unit for scenario 1 with inlet conditions as
mentioned in section 2.2 and thermodynamic methodology mentioned in section 3.

5.8 t/h anode copper

6.95 t/h black copper 06.85
t/h t/h black
metal copper
oxide

1.9 t/h carbon

9.76 t/h exhaust gas
Oxidation
9.1 t/h oxygen
1.2 t/h slag
0.63 t/h Flux
1.82 t/h Solid mono oxide

Figure 17: Mass balance on oxidation unit

4.1.2 Scenario 2
4.1.2.1 Reduction
The first stage in the process was feed into the furnace for reduction with feed conditions as
mentioned in section 2.2 and unit simulation conditions as mentioned in section 3 above. The
following outputs were obtained from FactSage that fulfil the requirements mentioned in section 1
of this report. Figure 18 below shows the plot of copper wt% in the melt as a function of
temperature at varying constant partial pressures of oxygen from 10 -6 to 10-12.

Figure 18: wt% copper in melt

16
The wt% of copper is found to decrease from 90% to 80% with an increase in temperature from
1100C to 1600C and a decrease in the partial pressure of oxygen. A requirement of the process being
that the wt% of copper in the melt be above 80%, a partial pressure of 10-11 atm and a temperature
of 1300C seems feasible. Higher temperatures would incur additional operational costs and a lower
wt% of copper being found in the melt, which would be counterintuitive to the increase in costs. The
process condition of 10-11 atm oxygen partial pressure and a temperature of 1300C yields a copper
wt% of 84.2%. Operating the reduction unit at lower temperatures would increase the wt% of
copper in the melt and utilise a lower amount of energy.

Although the highest purity of the black copper can be obtained through reduction at high oxygen
partial pressure, this condition is quite undesirable as it promotes high copper loss into the slag as
Cu2O. The copper loss into the slag phase at various reducing conditions ranging from an oxygen
partial pressure of 10-7 atm to 10-10 atm and at temperatures varying from 1100C to 1300C, and the
result is shown Figure 19, where It can be seen that the copper loss to the slag decreases from 30 wt
% to 5 wt% as the temperature increases and the pressure decreases. Therefore, to reduce the
copper loss to the slag, a feasible point would be the operate at 1300C at a partial pressure of 10 -11,
where the loss of copper is approximately 0.25 wt%.

Figure 19: wt% Cu2O in melt

A low carbon dioxide wt% and high copper recovery are also key requirements in this report. Figure
20 below shows that the recovery of copper increases from 90% to approximately 100% as the
temperature increases from 1100C to 1600C and the partial pressure decreases. However, at lower
temperatures higher amounts of carbon dioxide is produced a more copper is lost to the slag phase.
As the pressure decreases the recovery of copper tends to increase. At a temperature of 1300C and
a partial pressure of 10-11 atm copper recovery is found to be the highest at approximately 100%,
therefore this condition is highly desirable.

17
 Figure 20: Recovery of copper

Figure 21 below shows the wt% of carbon dioxide in the gas phase decreasing as the temperature
increases and the partial pressure decreases. Therefore, the chosen operating point being a
temperature of 1300C and a partial pressure of 10 -11 atm is feasible and produces approximately 20
wt% of carbon dioxide at this operational point, which is reasonably low. Increasing the temperature
further would decrease the amount of carbon dioxide produced but would result in higher
operational costs for a slight decrease in wt% of carbon dioxide produced.

4.1.2.2 Oxida
tion

Figure 21: wt% CO2

Following the reduction stages is the oxidation stage with FactSage simulation conditions mentioned
in section 3 of the report and outputs graphically shown below.

18
As shown in Figure 22 the wt% of copper in the melt increases with more oxidation stages, this is
due to the impurities being removed from the black copper, increasing the purity. At higher
temperatures the wt% of copper in the melt is found to be higher with an increase in the oxidation
stage. At stage 7 of oxidation the wt% of copper is found to be the highest, above 90%.

105

100

95

90
Wt% Cu

85

80

75

70
1 2 3 4 5 6 7 8 9 10

Oxidation stage

T=1100 T=1200 T=1300 T=1400 T=1500 T=1600

Figure 22: wt% copper

However, as seen in Figure 23, oxidation after stage 6 results in a high loss of copper to the slag
phase as Cu2O, which is an undesirable condition. Oxidation at stage 6 seems feasible, at a
temperature 1300C the wt% of Cu 2O is found to be 1.43%, which is also below the requirement of
1.5 wt%. 90

Lower 80

70

60

50
Wt% Cu2O

40

30

20

10

0
1 2 3 4 5 6 7 8 9 10

Oxidation stage

T=1100 T=1200 T=1300 T=1400 T=1500 T=1600

temperatures and oxidation stages would lower the copper losses to the slag phase and reduce the
Figure 23: wt% Cu2O
energy consumption as well. However, as can be seen by Figure 24,Figure 27,Figure 25 and Figure
26, lower temperatures result in a lower removal of impurities which is undesirable. Therefore,
operating at 1300C and an oxidation stage of 6 is preferred. Figure 27 shows that the wt% of Zn
decreases from 3.5 wt% to 1.1 wt% at 1300C, which suggests a substantial removal in impurities by
19
removal of zinc. Figure 24 shows that Fe in the melt follows the same trend of decreasing oxidation
stage 1 to stage 10 for al temperatures. At 1300C, the wt% of Fe decreases from 3 wt% to 0.22 wt%,
which is suggestive that this is a feasible operating condition due to the large removal of Fe as an
impurity. Figure 25 shows that the wt% of Pb after oxidation decreases with the oxidation stage by a
small amount followed by a drastic decrease after an oxidation stage of 6, however, after stage 6 a
large amount of copper is lost to the slag phase. Therefore, it is preferrable to operate at an
oxidation stage of 6. Higher temperatures also result in a reduced amount of Pb removal. At 1300C,
the wt% of Pb drops from 7.9% to 7%. This is not a substantial amount, which is due to Pb being
relatively less reactive with oxygen and as a result further processing would need to be done to
further remove impurities after oxidation. Figure 26 shows that sulphur initially present in the
product is of low content and decreases from 0.003 wt% to 0.0026 wt%. Further processing would
need to be done to remove the sulphur after oxidation. At higher temperatures and higher oxidation
stages sulphur can be completely removed, however this results in more copper being lost to the
slag phase, therefore this condition is not feasible.
3.5 9

8
3
7
2.5
6
2 5
Wt% Fe

Wt% Pb

1.5 4

3
1
2
0.5
1

0 0
1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10
Oxidation stage Oxidation stage

T=1100 T=1200 T=1300 T=1400 T=1500 T=1600 T=1100 T=1200 T=1300 T=1400 T=1500 T=1600

Figure 24: wt % Fe Figure 25: wt% Pb

4 0.004

3.5 0.0035

3 0.003

2.5 0.0025

2 0.002
Wt% Zn

Wt% S

1.5 0.0015

1 0.001

0.5 0.0005

0 0
1 2 3 4 5 6 7 8 9 10 1 2 3 4 5 6 7 8 9 10

Oxidation stage Oxidation stage

T=1100 T=1200 T=1300 T=1400 T=1500 T=1600 T=1100 T=1200 T=1300 T=1400 T=1500 T=1600

Figure 27: wt% Zn Figure 26: wt% S

Figure 28 below shows that the wt% of Ni increases with an increase in oxidation, this suggests that
other impurities are being removed from the melt but not Ni, which is due to the low reactivity of Ni
with oxygen relative to other impurities. Further processing such as electrolytic refining would need
to be done after oxidation to remove Ni. At 1300C, the wt% of Ni increases from 2.8 wt% to
approximately 3 wt%. increasing the oxidation stage would result in complete removal of Ni,

20
however this also results in a higher loss of copper to the slag phase. Therefore, operating at stage 6
is preferred.

3.5

2.5

2
Wt% Ni

1.5

0.5

0
1 2 3 4 5 6 7 8 9 10

Oxidation stage

T=1100 T=1200 T=1300 T=1400 T=1500 T=1600

Figure 28: wt% Ni

Figure 29 below shows that the wt% of carbon dioxide increases as the oxidation stage increases and
the temperature decreases.

120

100

80
Wt% Co2

60

40

20

0
1 2 3 4 5 6 7 8 9 10

Oxidation stage

T=1100 T=1200 T=1300 T=1400 T=1500 T=1600

Figure 29: wt% CO2

At 1300C
carbon dioxide wt% increases from 0% to 83%, lower oxidation stages would result in a lower
quantity of carbon dioxide production however fewer impurities would be removed. Therefore, the
production of carbon dioxide is compromised for the removal of impurities.

21
 4.1.2.3 Mass Balance Schematic
Considering section 4.1.2.1, the optimum conditions for the reduction unit was chosen to be 1300C
with a partial pressure of oxygen as 10 -11 atm, A mass balance shown below is done at this operating
condition.

Figure 30Figure 16 below shows the mass balance on the reduction unit for scenario 1 with inlet
conditions as mentioned in section 2.2 and thermodynamic methodology mentioned in section 3.

12 t/h Scrap
10.9 t/h black copper

0.36 t/h exhaust gas

0.425 t/h slag
Reduction
1.24 t/h slag

0 t/h Metal & oxide dust

0.075 t/h Coke

Figure 30: Mass balance on reduction unit

Considering section 4.1.2.2, the optimum conditions for the oxidation unit was chosen to be 1300C
at stage 6 oxidation, A mass balance shown below is done at this operating condition.

Figure 31 below shows the mass balance on the oxidation unit for scenario 1 with inlet conditions as
mentioned in section 2.2 and thermodynamic methodology mentioned in section 3.

10.9 t/h black copper 9.5 t/h anode copper

2 t/h carbon
12.7 t/h exhaust gas
Oxidation
9.55 t/h oxygen

0.678 t/h Flux 0.9 t/h slag

Figure 31: Mass balance on oxidation unit

4.2 Energy Balance

Assuming no work done in neither the reduction nor the oxidation units,

ṁ ( hout −h¿ ) =Q

22
Therefore, the heat transfer between the unit and the environment is equal to the change in
enthalpy since the total mass entering the units is also equal to the mass leaving the units.

4.2.1 Scenario 1
4.2.1.1 Reduction
For the optimally chosen conditions of T = 1300C and a partial pressure of 10-12 the change in
enthalpy is found to be -3.46e10.

The reduction and oxidation process in the black copper route is an exothermic process, which
means it releases heat. The heat is generated by the oxidation of coke, which is used as a reducing
agent, and this heat is used to maintain the high temperature required for the reaction to occur. The
reduction reaction of copper oxide to copper metal is an exothermic reaction, which means it
releases energy in the form of heat. This heat, along with the heat generated from the oxidation of
coke, is used to sustain the high temperatures required for the reaction to proceed. The reduction
process for black copper smelting is exothermic, meaning it releases heat. Therefore, the process
does not require external energy input for the reduction stage. However, some energy may be
required for heating up the reactor initially and to maintain the desired temperature range during
the process.

4.2.1.2 Oxidation
For the optimally chosen oxidation unit conditions of T=1300C and oxidation stage of 3 the change in
enthalpy is found to be -6e9.

The oxidation process is exothermic, meaning it releases heat. During the oxidation stage, controlled
oxidation is used, and oxygen-rich air is injected into the reactor. This oxidizes the impurities from
the liquid copper and separates them into the slag and vapor 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). As a result, these impurities are removed from the black copper during the
oxidation process, and the heat released during the oxidation process can be recovered for use in
subsequent stages of the process.

4.2.2 Scenario 2
4.2.2.1 Reduction
For the optimally chosen conditions of T = 1300C and a partial pressure of 10-11 the change in
enthalpy is found to be 4.42e9.

The oxidation process in scenario 2 is endothermic, meaning it absorbs heat. The heat generated by
the oxidation of coke is insufficient and additional external heat would need to be supplied to the
unit for the reaction to occur. This is because there was no waste PCB in scenario 2 to provide heat
through combustion reactions. So, the heat needed for the reduction process must be supplied
externally.

23
4.2.2.2 Oxidation
For the optimally chosen oxidation unit conditions of T=1300C and oxidation stage of 6 the change in
enthalpy is found to be -5.37e10

In scenario 2, where no PCB is supplied to the reduction process, the oxidation unit releases heat.
This is because the absence of PCB results in a reduction of the amount of organic material that
needs to be oxidized, thereby reducing the demand for oxygen. As a result, less air needs to be
injected into the reactor for the oxidation process, and the exothermic oxidation reaction releases
heat energy. This is since the oxidation of black copper is an exothermic reaction. When the
impurities in the black copper are oxidized, heat is released as a by-product of the chemical reaction.
In scenario 2, since less oxygen is required for the oxidation process, less air needs to be injected
into the reactor, resulting in less heat being required to maintain the desired temperature. This
excess heat can be utilized in the process or recovered for other uses. Therefore, the process does
not require external energy input for the reduction stage. However, some energy may be required
for heating up the reactor initially and to maintain the desired temperature range during the
process.

4.3 Flowsheet
Figure 32 below shows the detailed flowsheet of the black copper route analysed in this report. The
mass balances for each stream is given in section Results and Discussion4 of this report.

Figure 32: Detailed flowsheet of process

24
5 Conclusion

The report utilized FactSage thermodynamic modelling to compare two scenarios for secondary
copper smelting, with only the first scenario utilizing PCBs as an input material. The results showed
that a temperature of 1300°C and an oxygen partial pressure of 10 -12 atm were suitable for
processing PCBs in scenario 1, while a temperature of 1300°C and an oxygen partial pressure of 10 -11
atm were optimal for scenario 2. Scenario 1 yielded 82.92 wt% copper, 0.086 wt% gold, 0.121 wt%
Cu2O, and 5.21 wt% CO2, with a copper recovery of 99.86%. In contrast, scenario 2 yielded 84.17 wt
% Cu, 0.25 wt% Cu2O, and 19.95 wt% CO2, with a copper recovery of 99.99%. These findings suggest
that scenario 2 is more suitable for copper extraction. However, scenario 1 contained valuable
materials, including gold, and the PCB waste input stream contained carbon, which could be used as
fuel and reductant in the reduction stage. On the other hand, scenario 2 supplied carbon in the feed
material, which generated heat and acted as a reducing agent. The presence of carbon in the PCB
waste input stream in scenario 1 could partially replace coke and result in better economic revenue
and reduced environmental impact. Therefore, the choice between the scenarios depends on the
priorities of the process, with scenario 2 being more suitable for copper extraction, and scenario 1
offering potential economic and environmental benefits.

6 References

Maryam Ghodrat, M. A. (2017). Thermodynamic analysis of metals recycling out of waste printed .

25
Appendix A. Inlet Stream Compositions

Table 1: Copper scrap composition

Copper Scrap Composition

Metal/Metal Cu Cu2O PbO ZnO NiO SnO2
Oxides
Wt% 70 7 8 5 5 5

Table 2: Slag/flux composition

Slag/Flux Composition
Component FeO CaO SnO2

Wt% 70 7 5

Table 3: Coke composition

Coke Composition
Elements C H2O S Al2O3 FeO
Wt% 90 5 0.8 2 2.2

Table 4: PCB composition

PCB composition
Elements Cu Au Ag Al Zn Pb Fe Ni Sn Br N C Al2O3 SiO2
Wt% 20 0.1 0.2 5 4 6 8.7 2 5 4 5 10 6 24

26