Precious Metal Recovery

School of Engineering
Department of Materials Science and Metallurgical Engineering
Final report:
Precious metal recovery from waste electrical and electronic equipment
by
Elria Maré
Abstract
The recovery of metals from shredded printed circuit boards using hydrometallurgical routes has been
investigated, with a specific focus on the recovery of Cu, Pd, Ag and Au. The leaching efficiencies of
various cyanide-alternative lixiviants, such as hydrochloric acid and thiourea, was investigated. A sulfuric
acid pre-treatment leaching step yielded Cu leaching efficiency of 96%, Pd 71%, Ag 34% and Au leaching
efficiency of 13%. The residue from the pre-treatment step was then leached in hydrochloric acid, which
gave leaching efficiencies of 95% Cu, Pd 82%, Ag 70% and Au 33%. The low recovery of Ag was
attributed to the precipitation of AgCI. In contrast, leaching of the sulfuric acid leach residue in thiourea
did not yield any significant leaching efficiencies, with leaching efficiencies of 16% Cu, Pd 11%, Ag 9%
and Au 14%. The results suggest that the hydrochloric acid lixiviant yielded higher leaching efficiencies
than that of the thiourea lixiviant.
Keywords: [Precious metals, Hydrometallurgical processing, Leaching, Printed circuit boards]
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Content
1. INTRODUCTION ......................................................................................................... 1
2. LITERATURE............................................................................................................... 1
2.1 Waste electric and electronic management ................................................................................................... 1

2.1.1 Waste management in South Africa ..........................................................................................................................1
2.2 Chemical analysis and pre-treatment of printed circuit boards ............................................................ 2
2.3 Current processing strategies ............................................................................................................................. 2
2.4 Hydrometallurgical route ..................................................................................................................................... 3

2.4.1 Sulfuric acid leach .............................................................................................................................................................3
2.4.2 Chloride leach of palladium, gold and silver .........................................................................................................4
2.4.3 Thiourea leach ....................................................................................................................................................................5
3. EXPERIMENTAL PROCEDURE................................... ERROR! BOOKMARK NOT DEFINED.
3.1 Safety and apparatus.......................................................................................... Error! Bookmark not defined.
3.2 Feasibility of experiment ................................................................................. Error! Bookmark not defined.
3.3 Experimental plan ............................................................................................... Error! Bookmark not defined.
3.4 Leaching efficiency ............................................................................................. Error! Bookmark not defined.
3.5 Sulphuric acid leach of Cu ................................................................................ Error! Bookmark not defined.
3.6 Chloride leach of palladium, gold and silver ............................................. Error! Bookmark not defined.
3.7 Thiourea leach of gold and silver .................................................................. Error! Bookmark not defined.
3.8 Aqua regia .............................................................................................................. Error! Bookmark not defined.
3.9 Scanning electron microscope sample preparation ............................... Error! Bookmark not defined.
4. RESULTS AND DISCUSSIONS .................................... ERROR! BOOKMARK NOT DEFINED.
4.1 Sulfuric acid leach ............................................................................................... Error! Bookmark not defined.
4.2 Hydrochloric acid leach .................................................................................... Error! Bookmark not defined.
4.3 Thiourea leach ...................................................................................................... Error! Bookmark not defined.
5. CONCLUSIONS AND RECOMMENDATIONS ................................................................. 6
6. ACKNOWLEDGEMENTS .............................................................................................. 7
7. REFERENCES .............................................................................................................. 7
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ANNEX A: PROJECT SCHEDULE........................................ ERROR! BOOKMARK NOT DEFINED.
A.1 Project GANTT Chart ............................................................................................. Error! Bookmark not defined.
A.2 Project target dates ............................................................................................... Error! Bookmark not defined.
A.3 Experimentation GANTT chart .......................................................................... Error! Bookmark not defined.
A.4 Experimentation target dates ............................................................................ Error! Bookmark not defined.
ANNEX B: DECLARATION ON PLAGIARISM ...................... ERROR! BOOKMARK NOT DEFINED.
ANNEX C: RESULTS ......................................................... ERROR! BOOKMARK NOT DEFINED.
List of Figures
Figure 1: Proposed flow sheet for the recovery of precious metals from shredded printed circuit
boards. ..................................................................................................... Error! Bookmark not defined.
Figure 2: Experimental setup of the sulfuric acid leaching test ............... Error! Bookmark not defined.
Figure 3: Experimental setup of hydrochloric acid leach. ........................ Error! Bookmark not defined.
Figure 4: Experimental setup of the thiourea leach ................................. Error! Bookmark not defined.
Figure 5: Aqua regia once sample is added ............................................ Error! Bookmark not defined.
Figure 6: Leach residue of all the experiments before scanning electron microscope analysis ..... Error!
Bookmark not defined.
Figure 7: Original feed material before scanning electron microscope analysis .... Error! Bookmark not
defined.
Figure 8: The original leaching solution after drying ............................... Error! Bookmark not defined.
Figure 9: Leach solutions after being mixed with a saturated salt solution and dried ...Error! Bookmark
not defined.
Figure 10: Average leaching rate during sulfuric acid leach ................... Error! Bookmark not defined.
Figure 11: Influence of hydrogen peroxide addition on the reaction temperature.. Error! Bookmark not
defined.
Figure 12: Scanning electron microscope analysis at 20kV of original feed material ...Error! Bookmark
not defined.
Figure 13: Scanning electron microscope analysis at 20kV of sulfuric acid leach residue ............. Error!
Figure 14: Energy Dispersive X-Ray Spectroscopy profile of leach residue after sulfuric acid leach
................................................................................................................. Error! Bookmark not defined.
Figure 15: Scanning electron microscope analysis at 20kV of original sulfuric acid leach solution Error!
Figure 16: Scanning electron microscope analysis at 20kV of original sulfuric acid leach solution after
being mixed with a saturated sodium chloride solution ........................... Error! Bookmark not defined.
Figure 17: Energy Dispersive X-Ray Spectroscopy profile of the sulfuric acid leach solution ........ Error!
Figure 18: Average leaching rate of the target elements during hydrochloric acid leach ............... Error!
Figure 20: Scanning electron microscope analysis at 20kV of hydrochloric acid leach residue ..... Error!
Figure 21: Energy Dispersive X-Ray Spectroscopy profile of leach residue after hydrochloric acid
leach ........................................................................................................ Error! Bookmark not defined.
Figure 22: Scanning electron microscope analysis at 20kV of original hydrochloric acid leach solution
Figure 23: Scanning electron microscope analysis at 20kV of original hydrochloric acid leach solution
after being mixed with a saturated sodium chloride solution ................... Error! Bookmark not defined.
Figure 24: Energy Dispersive X-Ray Spectroscopy profile of saturated leach solution after hydrochloric
acid leach................................................................................................. Error! Bookmark not defined.
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Figure 25: Average leaching rate of the target elements over the total leaching time during thiourea
Figure 27: Scanning electron microscope analysis at 20kV of thiourea leach residue .Error! Bookmark
not defined.
Figure 28: Scanning electron microscope analysis at 20kV of original thiourea leach solution ...... Error!
Figure 29: Scanning electron microscope analysis at 20kV of original thiourea leach solution after
being mixed with a saturated sodium chloride solution ........................... Error! Bookmark not defined.
Figure 30: Energy Dispersive X-Ray Spectroscopy profile of saturated leach solution after thiourea
Figure 31: Proposed project schedule for NSC 422. ............................... Error! Bookmark not defined.
Figure 32: Proposed scheduling for experiments. ................................... Error! Bookmark not defined.
List of tables
Table 1: Copper yield with different combinations of reagents (Quinet et al., 2005) .............................. 4
Table 2: Chemical composition after chloride leach ................................................................................ 5
Table 3: Reagents and equipment required for the project (Glassworld, 2019) .... Error! Bookmark not
defined.
Table 4: Initial chemical composition ....................................................... Error! Bookmark not defined.
Table 5: Main fractions of feed material (UIS, 2018) ............................... Error! Bookmark not defined.
Table 6: Hydrogen peroxide addition schedule during sulfuric acid leach(Quinet et al., 2005) ...... Error!
Table 7: Hydrogen peroxide addition schedule during hydrochloric acid leach(Quinet et al., 2005)
Table 8: Sample retrieval rate during the thiourea leaching step ............ Error! Bookmark not defined.
Table 9: Summary of leaching conditions (Aylmore, 2005), (Quinet, et al., 2005) (Engelbrecht, 2018)
Table 10: Leaching efficiency of sulfuric acid leach ................................ Error! Bookmark not defined.
Table 11: Chemical composition of feed material and the leach residue after the sulfuric acid leach
Table 12: Leaching efficiency of hydrochloric acid leach ........................ Error! Bookmark not defined.
Table 13: Chemical composition of sulfuric acid leach residue and the hydrochloric acid leach residue
Table 14: Leaching efficiency during thiourea leach ............................... Error! Bookmark not defined.
Table 15: Chemical composition of sulfuric acid leach residue and the thiourea leach residue ..... Error!
Table 16: Preliminary due dates for NSC 422. ........................................ Error! Bookmark not defined.
Table 17: Expected dates on which experiments will be carried out and their duration. ................ Error!
Table 18: Chemical composition of sulfuric acid leach solution .............. Error! Bookmark not defined.
Table 19: Chemical composition of hydrochloric acid leach solution ...... Error! Bookmark not defined.
Table 20: Chemical composition of thiourea leach solution .................... Error! Bookmark not defined.
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1. Introduction
Waste electric and electronic equipment (WEEE) is a rapidly growing waste stream globally, the
exponential growth rate of this waste stream is generally attributed to the availability of new equipment
and devices that are outfitted with the latest gadgets and technology. One of the most notable trends that
is responsible for the ever-growing waste stream is the speed at which the global information society is
expanding. This trend is characterised by the growing demand for innovation, improved efficiency as well
as social and economic development.
Research by Baldé et al. (2017) found that the annual WEEE waste generated in 2016 was 44.7 million
tonnes globally. It is expected that the waste stream will grow to 52.2 million tonnes by 2021. Of the 44.7
million tonnes WEEE waste generated during 2016, only 20% has been recycled.
Nearly all WEEE contain at least a single printed circuit boards (PCB), which in turn has a high
concentration of precious metals. It has been approximated that up to 6% of the WEEE, consists of PCBs,
which shows the most promise in terms of profitable recycling. These PCB can contain up to twenty
different metals including precious metals, base metals as well as toxic metals (Cucchiella et al., 2015).
South African companies such as eWASA have formed an e-waste management system that aims at
managing e-waste in the most effective way while focusing on following sustainable and environmentally
sound recycling routes. Since being established in 2008, this company has grown exponentially, with over
1000 collections points being established across the country. It has been reported that 17 733 tonnes of
WEEE were collected in 2015 alone (eWASA, 2019). Initiatives such as this are needed if WEEE recycling
in South Africa is to become sustainable and eventually competitive in international markets.
2. Literature
2.1 Waste electric and electronic management

WEEE management is usually categorised into the following three scenarios namely, official take-back
system, mixed residual waste and any collection outside the official take-back system. Countries that have
a national waste management system in place usually have contracted waste companies that collect all
the relevant waste. The waste is then distributed to metal and plastic recycling companies, specialised
WEEE recycling companies or might even be processed for exportation (Baldé et al., 2017).
2.1.1 Waste management in South Africa

It has been found that the most WEEE generated in South Africa comes from the government sector and
the business sector, with a recent increase in WEEE generated from households. It has been suggested
by Lydall et al. (2017) that 300 000 tonnes of WEEE are generated with only 18% being recycled. It has
been found that the majority of the WEEE being generated in South Africa hails from Gauteng (45%)
followed by the Western Cape (20%) and Mpumalanga (10%). The value chain of WEEE within South
Africa is divided into four main sections namely; collection, dismantling, pre-processing and end
processing. The formal WEEE recycling industry in South Africa is dominated by a few well-established
companies that specialise in the collection, dismantling and pre-processing. Over the past 5 years,
multiple medium-sized companies have also moved into this industry, focussing on location-specific
collection combined with dismantling services. One of the major advantages that are associated with
operating within these sectors is that minimum specialised technology and highly skilled labour is required
(Lydall et al., 2017).
It is generally accepted within the WEEE recycling sector that the collection and pre-processing of WEEE
is not a sustainable venture but is rather treated as a complementary activity. In order to make the process
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profitable, most WEEE is refurbished and then resold. It has been reported that the sale of refurbished
WEEE can comprise up to 60% of small and medium-sized businesses annual revenues. PCBs are
generally exported for end-processing to processing plants in Europe. A few small and medium-sized
companies sell whole PCBs to SA Precious metals Ltd for further processing. Plastics from WEEE is often
shredded and then sold to plastic manufacturing companies in relatively small volumes, there is a
consensus that processes that use WEEE plastic should be further investigated in South Africa (Lydall et
al., 2017).
The conclusion has been made that the success of WEEE recycling in South Africa is not limited by
technology but rather by the availability of constant WEEE volumes that is introduced into the local
recycling stream on a regular basis (Lydall et al., 2017).
2.2 Chemical analysis and pre-treatment of printed circuit boards

The chemical composition of PCBs can vary greatly depending on the age, function and manufacturer of
the PCB. Currently, no standard procedure exists to determine the chemical composition of PCB, this is
further complicated by the extreme diversity in terms of typical PCBs currently found on the market. In
order to design an optimised metal recovery process from WEEE, more specifically PCBs, the chemical
composition of the PCBs being used as feed material in the process has to be relatively similar. The
recycling process is further complicated by the presence of plastics and ceramics in PCBs. It is widely
accepted that the best analysis technique for determining the chemical composition of PCBs is using wet
spectroscopy techniques such as inductive coupled plasma (ICP) or atomic spectroscopy tests after being
dissolved (Ogunniyi et al., 2009).
The pre-treatment of the PCBs often includes a dismantling step and a pre-leaching step. In the case of
the dismantling step, either an automatic or manual route can be followed depending on the WEEE being
processed. By dismantling the WEEE, the PCB stream is effectively concentrated in terms of valuable
metal, while simultaneously removing any hazardous components. It has been found that shredded PCBs
often delivers higher recovery yields, justifying an additional shredding step (Tuncuk et al., 2012).
It has been found by Zhang and Forssberg (1997) that PCBs that are shredded to size fractions smaller
than 2mm achieve a maximum metal recovery yield. It is advisable to avoid any milling when working with
PCBs, Ogunniyi et al. (2009) found that the recovery of metals drastically decreased if the PCBs were
milled to size fractions smaller than 75µm.
In recent years a pre-leaching step has also been employed to leach out the bulk of the copper (Cu)
present within the shredded PCBs using low-cost leaching media. By leaching out easily leachable metals
such as Cu out of the PCB feed material using low-cost leachants, the overall reagent costs of the leaching
processes are decreased. This results in the expensive leachants being used to leach out the target
metals such as gold (Au) and palladium (Pd) which is prone to form insoluble complexes (Quinet et al.,
2005).
2.3 Current processing strategies

There is a wide variety of processing strategies for recovering metals from WEEE, the most notable being
hydrometallurgical processing, physical and mechanical separation techniques, pyrometallurgical routes
and microwave treatments. With pyrometallurgical route and the hydrometallurgical processing
dominating in industry. One of the most viable processing options currently available is a combination of
a mechanical separation step and hydrometallurgical processing (Zhanga et al., 2012).
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Following a study by both Mintek and Rand Refinery Ltd, it was found that pyrometallurgical processing
routes are not feasible within South Africa. It was found that South Africa does not have a constant supply
of WEEE at a large enough volume to make a pyrometallurgical plant economically feasible. It is for this
reason that hydrometallurgical processing routes are preferred in South Africa. Hydrometallurgical
processing plants have the distinct advantage of being able to operate on a small scale while having the
potential to increase the capacity of the plant if required. Other advantages include lower capital costs
while simultaneously delivering higher metal recovery yields. Hydrometallurgical routes are also
considered to be more environmentally sustainable than pyrometallurgical routes (Lydall et al., 2017).
2.4 Hydrometallurgical route

The hydrometallurgical processing route for metal recovery from PCBs is usually divided into the following
steps. Firstly, the WEEE is subjected to a pre-treatment step that usually involves some form of
dismantling as well as a size reduction step, the most popular size reduction technique in industry is to
shred the PCBs to a size fraction of less than 2mm but more than 75µm. After the PCBs has been
shredded the bulk of Cu present in the PCB feed material is leached out using a low-cost leachant. This
pre-leaching step is included to decrease the overall reagent costs during the experiment while
simultaneously increasing the leaching selectivity of the target elements when using the more expensive
leaching mediums. The leach reside after the pre-leach stage is then subjected to multiple leaching stages
before ending with a purification or precipitation step (Zhanga et al., 2012).
2.4.1 Sulfuric acid leach

It has been found that PCBs generally contain very high quantities of Cu, which is known for its relative
ease at being leached out. By using a low-cost leaching media such as sulfuric acid (H2SO4), the bulk of
the Cu can be leached out as cost-effectively as possible. This step is generally considered to be the pre-
leaching stage. Research by Quinet et al. (2005) investigated several oxidising agents to be used in
combination with the H2SO4 leaching media when leaching PCBs. The oxidising agents most often used
in industry is ferric iron (Fe3+), oxygen and hydrogen peroxide (H2O2). All three of these oxidising agents
were investigated and compared. The chemical reactions taking place during the different leaching
combinations are described below in equations 1, 2 and 3.
Cu + Fe2(SO4)3(ag) ⇌ CuSO4(aq) + 2FeSO4(aq) (1)
Cu + 0.5O2(g) + H2SO4(aq) ⇌ CuSO4 + H2O (2)
Cu + H2O2 + H2SO4(aq) ⇌ CuSO4 + 2H2O (3)
The leaching conditions as described by equation 1 was again conducted using a 2 M H2SO4 solution
with 0.015 M Fe3+ as the oxidising agent. During the leaching experiment where Fe3+ was used as an
oxidising agent, the observation that silver (Ag) will only be dissolved in these leach conditions if the
concentration of Fe3+ is more than 0.01 M as proposed by Choi et al. (1991) was confirmed. The leach
tests were conducted to find optimal leach conditions when leaching Cu out of PCBs. The leach conditions
as described by equation 2 was conducted by using a solution of 2 M H2SO4 and blowing 80 l/kg/h oxygen
through the solution. All the leach experiments were conducted at a 5:1 pulp dilution for a total leach time
of 3 h.
The leach results from both these leaching combinations as described above did not yield metal
recoveries in excess of 90%. This justified the investigation into using H2O2 as an oxidising agent despite
the high costs involved. The final leaching conditions involved 2 M H2SO4 and 53.5 kg/t H2O2 within the
leach solution. In order to maintain optimised oxidising conditions throughout the leach experiment, the
H2O2 is continuously added during the experiment. The pH at the end of the H2SO4 and H2O2 leach
combination was recorded as 0.32, the very acidic conditions have been found to promote the recovery
of the dissolved metals from the leach solution. This leach combination provided the only leach conditions
3
with a metal recovery yield in excess of 90%. In an attempt to decrease the reagent costs the following
combination of H2SO4 and H2O2 concentrations were compared to the Cu yield, the leach data as
determined by Quinet et al. (2005) are summarised in Table 1.
Table 1: Copper yield with different combinations of reagents (Quinet et al., 2005)
H2SO4(M) H2O2 (kg/t) Copper yield (%) pH
2 368 96.4 -0.31
1.5 197 98.5 0.04
1.2 93.6 99.2 0.27
1.2 53.5 98.5 0.32
The most cost-effective leaching combination, from Table 1 was found as 1.2 M H2SO4 and 53.5 kg/t H2O2
combination that delivered a Cu yield of 98.5%. In order to further optimise the leaching process, H2O2
is added in 15 min intervals throughout the total leach time of 3 h to create and maintain sufficiently
oxidising leaching conditions that are required to leach the metals from the PCBs (Quinet et al., 2005).
2.4.2 Chloride leach of palladium, gold and silver

Once most of the Cu is removed from the leach residue, the following leaching stages target precious
metals such as Pd, Ag and Au. It is advisable to ensure that the leaching conditions are maintained at a
minimum reduction potential of 0.53V in order to be able to oxidise Pd. The choice of chloride media has
traditionally been limited to HCI, NaCI and NH4CI. Of these choices, HCI and NaCI are favoured by
industry. In order to determine the Pd yield during these leaching conditions, both 2 M HCI and 2 M NaCl
were tested by Quinet et al. (2005). During the experiments, it was found that HCI yielded a Pd recovery
of 93% as opposed to the 67% recovered by NaCI. This confirms that the dissolution rate of Pd is
enhanced in acid conditions as can be seen in equation 5
During the HCI leach, only two oxidising agents were investigated namely nitric acid (HNO3) and H2O2.
The reduction potential of the oxidising agents is 0.96V and 1.77V respectively, indicating that both these
oxidising agents will be able to oxidise Pd. The chemical reactions taking place is represented by equation
4 and 5.
Pd + 2/3HNO3 + 4Cl− + 2H+ ⇌ PdCl42− + 2/3NO + 4/3H2O (4)
Pd + H2O2 + 4Cl− + 2H+ ⇌ PdCl42− + 2H2O (5)
Both the 75 kg/t HNO3 and 20.5 kg/t H2O2 were investigated in a 2 M HCI solution, yielding 94.8% Pd and
93.1% Pd respectively. In industry, the use of HNO3 as an oxidising agent is often avoided because of
the formation of nitrate-containing effluents and dangerous NO gas. This makes H2O2 the only viable
oxidant for these leaching conditions. In order to optimise the leaching conditions, H2O2 is added in 15
min intervals to maintain an oxidising environment while leaching. It has been found that Au, Cu and Pd
will also be dissolved during these leaching conditions. The Ag present usually precipitates as AgCI, as
seen in equation 6.
Ag+ + Cl− ⇌ AgCl (6)
The chemical composition of the leach solution and residue after the chloride leach, under ideal leaching
conditions as performed by Quinet et al. (2005) can be seen in Table 2.
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Table 2: Chemical composition after chloride leach
Cu Ag Au Pd
Leach solution (mg/L) 360 24 20 110
Leach residue (ppm) 202 4300 991 37
It is thus concluded from test work done by Quinet et al. (2005) that the ideal leaching conditions have
been found as 2 M HCI with 20.5 kg/t H2O2 which should be continuously added in 15 min intervals. The
leach time has been determined as 3 h while maintaining the leach solution temperature at 75°C, the ideal
pulp dilution has been found to be 3:1 (Quinet et al., 2005).
2.4.3 Thiourea leach

Environmental and health concerns have recently promoted the use of cyanide alternative lixiviants. Even
though cyanide is a very effective lixiviant, alternative lixiviants such as thiourea, thiosulfate and
thiocyanate have been investigated to act as a possible replacement for cyanide. The use of thiourea for
Au extraction is especially popular in underground and in-stope applications. Research has also recently
been done into the viability of using thiourea to treat refractory Au ores. Recently it has been discovered
that thiourea may possess possible carcinogenic properties, this effectively halted any research into
thiourea as a possible cyanide substitute in the mining sector. Despite this drawback, laboratory research
into thiourea is currently underway in Eastern Europe and China. It has also been concluded that thiourea
leaching is favourable when operating in acidic conditions (Aylmore, 2005).
The general leaching conditions for specifically thiourea leaching has been found to be 0.13 M thiourea
which is often combined with a thiourea stabiliser. Many thiourea stabilisers have been investigated and
the most effective one has been found to be Fe3+ with a concentration of 0.09 M. In order to optimise the
leaching conditions, it is recommended to maintain the pH of the leaching solution between 1-3 (Aylmore,
2005). The suggested gold dissolution rate when leaching with thiourea can be seen in equation 7.
Au + 2NH2CSNH2 + Fe3+ ⇌ [Au(NH2CSNH2)2]+ + Fe2+ (7)
The Au leaching rate is highly sensitive to pH and to the redox potential of the leaching solution. It has
been found that thiourea tends to rapidly decompose when exposed to substances that are unable to
leach Au. By maintaining the leaching conditions within the prescribed operating window, the stability of
the thiourea is greatly increased. Under such conditions, the thiourea decomposition will be reduced, while
simultaneously optimising the leaching of Au. It has been found that thiourea can form strong complexes
with base metals, specifically Cu, lead and zinc. This can ultimately lead to a higher thiourea consumption
rate. In order to limit the decomposition of thiourea during leaching, stabilisers such as sulphur dioxide,
sulphite and iron ions are added. In addition, it was found that the thiourea consumption can be further
decreased by simply washing the leached material with water, or with different concentrations of H2SO4.
This is dependent on the ore being processed. However, if the ore is pre-treated with acid prior to the
thiourea leaching step, then most of the leachable metals are removed while also allowing the thiourea to
stabilise quicker, thus limiting unnecessary reagent consumption. One of the main advantages that
thiourea leaching has over cyanide leaching is that no neutralisation step is needed when processing
acidic pre-oxidized sulphide ores, prior to it being leached by thiourea. The general relationship that was
observed is that reagent consumption is dependent on reagent concentration. Higher extraction costs are
thus expected when working with thiourea, as compared to cyanide leaching. Currently, thiourea is still
an unlikely industrial substitute for cyanide leaching in Au extraction since it has been discovered that
thiourea can be potentially carcinogenic. Several niche applications are currently being investigated, but
these are greatly restricted by the narrow operating window within which thiourea is stable. In order to
make thiourea a viable alternative option for Au extraction, lower concentrations of thiourea will have to
5
be used when leaching, in order to lower the overall operating costs. More research will have to be
conducted into thiourea leaching before it can be implemented into industry (Aylmore, 2005).
3. Conclusions and recommendations

The recovery of metals and more specifically precious metals from WEEE has recently become a more
sustainable processing method during the ever-increasing WEEE waste streams being generated
globally. Hydrometallurgical processing routes are often preferred over pyrometallurgical routes because
of higher metal recovery yields, lower capital costs and generally more environmentally sustainable
processing methods. The increased interest in the new processing possibilities available to recover metals
from WEEE justifies the investigation to find optimised and universal processing routes for WEEE. The
processing conditions investigated during this specific project compared the metal recovery yields of both
HCI leach and a cyanide alternative lixiviant, namely thiourea leach after a H2SO4 pre-leaching step.
The H2SO4 pre-leaching step delivered an overall high leaching efficiency of most of the target elements.
The target elements investigated during this project had the following leaching efficiencies namely, Cu
96%, Pd 71%, Ag 34% and Au 13%. The leaching efficiency of Au during the pre-leaching step is higher
than expected and has been attributed to the presence of Br in the form of the brominated flame-retardant
present in the feed material. Research by Zhanga et al. (2012) found that when Au is in solution with Br,
solubilised Au complexes can form. The leach rate of the H2SO4 leach is represented by Figure 10. It can
be seen from Figure 10 that the maximum leach rate is achieved for the majority of the target elements
after 60 min. Depending on the purpose of the leaching step, the ideal leach time can be changed from
270 min as suggested by Quinet et al. (2005) to 60 min. The decreased leach time will significantly reduce
the reagent costs and labour costs to name a few while maintaining a high metal recovery yield.
The HCI leaching step also delivered relatively high leaching efficiencies as seen during the H2SO4 leach
step. The leaching efficiency of the investigated metals during this leach step is Cu 95.00%, Pd 82%, Ag
70% and Au 33%. The leaching efficacy of all these elements was increased from the H2SO4 leach step.
The visual representation of the leaching rate throughout the leach experiment can be seen in Figure 18.
It can be seen from Figure 18 that the leach rates stabilised after 120 min, which is 60 min earlier than
the proposed 180 min stabilisation point by Quinet et al. (2005). The fluctuations in the leach rate of the
Ag in Figure 18 is attributed to the precipitation of AgCI during the leaching process. The increased leach
rate of Au is also attributed to the presence of Br still present within the feed material after the H2SO4
leach step.
The lowest leaching efficiencies experienced during the whole project was from the thiourea leaching
step. The leaching efficiencies during this step was found to be Cu 16%, Pd 11%, Ag 9% and Au 14%. It
is assumed that the leach conditions reached a passivation stage during the leaching experiment,
resulting in the very low leaching efficiencies. The leaching efficiency of Au is relatively close to the
leaching efficiency achieved during the H2SO4 leach; this suggests that the thiourea does influence the
leaching abilities of Au. If the leaching conditions are changed and possibly optimised it is expected to
see a significant increase in the leaching efficiency of Au.
The most successful leach step in terms of the investigated metals is the HCI leach. The significantly
higher leaching efficiencies achieved during the HCI leach step justifies the additional costs of the leach
step when compared to the thiourea leach step.
It is recommended to further investigate the optimised thiourea leaching conditions before a suitable
cyanide alternative lixiviant is chosen. Stronger ceramic stirrers are also suggested to ensure fully agitated
leach conditions for the HCI and thiourea leach step.
6
4. Acknowledgements
The feed material was supplied by Mintek. Dr J. Kabangu-Mpinga and Dr S. Lubbe carried out the ICP
analysis. Mr C. Coetsee helped with the SEM analysis. Mr D. Odendaal and Mr C. Kweto for assistance
during the project.
5. References
Antonijević, M., Dimitrijević, M. and Janković, Z., 1997. Leaching of pyrite with hydrogen peroxide in
sulphuric acid. Hydrometallurgy, 46(1), pp. 71-83.
Aylmore, M., 2005. Alternative lixiviants to cyanide for leaching gold ores. In: M. D. Adams, ed.
Developments in Mineral Processing,. Vancouver: Elsevier, pp. 501-539.
Baldé, C., Forti, V., Gray, V., Kuehr, R., and Stegmann, P., 2017. The Global E-waste Monitor 2017.
[Online] Available at: https://www.itu.int/en/ITU-D/Climate-Change/Documents/GEM%202017/Global-E-
waste%20Monitor%202017%20.pdf [Accessed 2 August 2019].
Choi, Y., Lee, E. and Han, K., 1991. The dissolution behavior of metals from Ag/Cu and Ag/Au alloys in
acidic and cyanide solutions. Metallurgical and Materials Transactions B , 22(6), pp. 755-764.
Cordis, 2017. Final Report Summary - HYDROWEEE DEMO (Innovative Hydrometallurgical Processes
to recover Metals from WEEE including lamps and batteries - Demonstration). [Online]
Available at: Final Report Summary - HYDROWEEE DEMO (Innovative Hydrometallurgical Processes
to recover Metals from WEEE including lamps and batteries - Demonstration) [Accessed 10 May 2019].
Cucchiella, F., D’Adamo, I., Koh, S. L. and Rosa, P., 2015. Recycling of WEEEs: An economic
assessment of present and future e-waste streams. Elsevier, Issue 51, pp. 263-272.
Cui, H. and Anderson, C., 2016. Literature Review of Hydrometallurgical Recycling of Printed Circuit
Boards (PCBs). Journal of Advanced Chemical Engineering, 6(1), pp. 1-11.
Cui, J. and Zhang, L., 2008. Metallurgical recovery of metals from electronic waste: A review. Journal of
Hazardous Materials, 158(2), pp. 228-256. Division of research safety, 2016. Aqua Regia. [Online]
Available at: https://drs.illinois.edu/SafetyLibrary/AquaRegia [Accessed 28 April 2019].
Engelbrecht, R., 2018. Copper recovery from Waste Electronic Equipment by a hydrometallurgical
process., Pretoria: University of Pretoria.
Erasmus, J., 2009. E-waste pilot project delivers. [Online] Available at:
https://www.brandsouthafrica.com/investments-immigration/economynews/e-waste-260209 [Accessed
10 May 2019].
eWASA, 2019. Welcome to eWASA. [Online] Available at: https://www.ewasa.org/ [Accessed 24
August 2019].
Glassworld, 2019. Glassworld. [Online] Available at: https://www.glassworld.co.za/chemicals.html
[Accessed 7 May 2019].
Indiamart, 2019. Printed Circuit Board Assembly. [Online] Available at:
https://www.indiamart.com/proddetail/printed-circuit-board-assembly-15114799333.html [Accessed 12
May 2019].
Investment Mine, 2019. Gold Investing. [Online] Available at: http://www.infomine.com/investment/gold/
Jadhav, U. and Hocheng, H., 2015. Hydrometallurgical Recovery of Metals from Large Printed Circuit
Board Pieces. Nature, pp. 1-10.
Kamberovic, Z., Korać, M. and Ranitović, M., 2011. Hydrometallurgical process for extraction of metals
from electronic waste-part ii: Development of the processes for the recovery of copper from printed
circuit boards (pcb). Association of Metallurgical Engineers of Serbia, 17(3), pp. 139-149.
Kamberović, Ž., Korać, M., Vračar, S. and Ranitović, M., 2010. Preliminary process analysis and
development of hydrometallurgical process for the recovery of copper from waste printed circuit boards.
Vienna, Going Green Care Innovation.
7
Kamberovic, Z., Ranitovic, M. and Korac, M., 2018. Hydrometallurgical Process for Selective Metals
Recovery from Waste-Printed Circuit Boards. MDPI, 8(441), pp. 1-19.
Klemencic, R., Kny, E. and Schmidt, W., 1989. Multilayer Circuit Boards with Molybdenum‐copper Metal
Cores. Circuit World, 15(4), pp. 5-8.
Lydall, M., Nyanjowa, W. and James, Y., 2017. Mapping South Africa’s Waste Electrical and Electronic
Equipment (WEEE) Dismantling, Pre-Processing and Processing Technology Landscape, Randburg:
Mintek.
Mahlalela, S., Tshazi, M. and Mostert, R., 2019. Safety and laboratory practice, Pretoria: University of
Pretoria.
Merck, 2019. Nitric acid. [Online] Available at:
https://www.sigmaaldrich.com/catalog/search?term=nitric+acid&interface=All&N=0&mode=match%20pa
rtialmax&lang=en&region=ZA&focus=product [Accessed 3 September 2019].
Ogunniyi, I., Vermaak, M. and Groot, D., 2009. Chemical composition and liberation characterization of
printed circuit board comminution fines for beneficiation investigations. Waste management (New York,
N.Y.), 29(7), pp. 2140-2146.
OurPCB, 2018. PCB Tinning-How Can I Get The Best Effect On The PCB. [Online]
Available at: https://www.ourpcb.com/pcb-tinning.html [Accessed 19 October 2019].
PCBcart, n/a. Application and Use of PCBs. [Online]
Available at: https://www.pcbcart.com/article/content/PCB-applications.html [Accessed 9 May 2019].
Quinet, P., Proost, J. and Van Lierde, A., 2005. Recovery of precious metals from electronic scrap by
hydrometallurgical processing routes. Minerals & Metallurgical Processing, 22(1), pp. 17-22.
Richter, F., 2017. These Countries Generate the Most Electronic Waste. [Online]
Available at: https://www.statista.com/chart/2283/electronic-waste/ [Accessed 9 May 2019].
ScienceABC, 2018. What is Aqua Regia? How does it dissolve gold?. [Online]
Available at: https://www.scienceabc.com/pure-sciences/aqua-regia-formula-recipe-structure-dissolve-
gold-platinum.html [Accessed 12 May 2019].
Sigma-Aldrich, 2019. Gold Standard for ICP. [Online]
Available at:
https://www.sigmaaldrich.com/catalog/search?term=gold+standard+icp&interface=All&N=0&mode=matc
h%20partialmax&lang=en&region=ZA&focus=product [Accessed 18 May 2019].
Sigma-Aldrich, 2019. Thiourea. [Online] Available at:
https://www.sigmaaldrich.com/catalog/search?term=thiourea&interface=All&N=0&mode=match%20parti
almax&lang=en&region=ZA&focus=product [Accessed 9 May 2019].
Swedish Chemicals Agency, 2019. Brominated flame retardants. [Online]
Available at: https://www.kemi.se/en/prio-start/chemicals-in-practical-use/substance-groups/brominated-
flame-retardants
[Accessed 11 September 2019].
Syed, S., 2012. Recovery of gold from secondary sources—A review. Hydrometallurgy, pp. 30-51.
Teodorescu, M., 2014. Top 10 engineering advancements of 21st century. [Online] Available at:
https://www.electronicproducts.com/Electromechanical_Components/Electromechanical_Switches/Top_
10_engineering_advancements_of_21st_century.aspx [Accessed 9 May 2019].
Tuncuk, A., Stazi, V., Akcil, A., Yazici, E. and Deveci, H., 2012. Aqueous metal recovery techniques
from e-scrap: Hydrometallurgy in recycling. Elsevier, pp. 28-37.
UIS, 2018. Analytical report, Pretoria: UIS.
Wilson, M., 2019. Tokyo's Olimpic medals are made from 47 tons of recycled electronics. [Online]
Available at: https://www.fastcompany.com/90304021/tokyos-olympic-medals-are-made-from-47-tons-
of-recycled-electronics [Accessed 9 May 2019].
XE Currency Converter, 2019. Live market rates. [Online]
Available at: https://www.xe.com/currencyconverter/convert/?Amount=1&From=USD&To=ZAR
8
XE, 2019. XE Currency Converter. [Online]
Available at: https://www.xe.com/currencyconverter/convert/?Amount=1&From=USD&To=ZAR
[Accessed 12 October 2019].
Zhanga, Y., Liu, S., Xie, H., Zeng, X. and Li, J., 2012. Current status on leaching precious metals from
waste printed. Procedia Environmental Sciences, Volume 16, pp. 560-568.
Zhang, S. and Forssberg, E., 1997. Mechanical separation-oriented characterization of electronic scrap.
Resources, Conservation & Recycling, 21(4), pp. 247-269.
Ziukaite, S., Tatariants, M., Denafas, G. and Ivanauskas, R., 2017. Feasibilities for hydrometallurgical
recovery of precious metals from waste printed circuit boards in Lithuania. Chemija, 28(2), pp. 109-116.

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School of Engineering

Department of Materials Science and Metallurgical Engineering

Keywords: [Precious metals, Hydrometallurgical processing, Leaching, Printed circuit boards]

2.1 Waste electric and electronic management ................................................................................................... 1

2.2 Chemical analysis and pre-treatment of printed circuit boards ............................................................ 2

2.3 Current processing strategies ............................................................................................................................. 2

2.4 Hydrometallurgical route ..................................................................................................................................... 3

3. EXPERIMENTAL PROCEDURE................................... ERROR! BOOKMARK NOT DEFINED.

3.1 Safety and apparatus.......................................................................................... Error! Bookmark not defined.

3.2 Feasibility of experiment ................................................................................. Error! Bookmark not defined.

3.3 Experimental plan ............................................................................................... Error! Bookmark not defined.

3.4 Leaching efficiency ............................................................................................. Error! Bookmark not defined.

3.5 Sulphuric acid leach of Cu ................................................................................ Error! Bookmark not defined.

3.8 Aqua regia .............................................................................................................. Error! Bookmark not defined.

4. RESULTS AND DISCUSSIONS .................................... ERROR! BOOKMARK NOT DEFINED.

4.1 Sulfuric acid leach ............................................................................................... Error! Bookmark not defined.

4.2 Hydrochloric acid leach .................................................................................... Error! Bookmark not defined.

4.3 Thiourea leach ...................................................................................................... Error! Bookmark not defined.

5. CONCLUSIONS AND RECOMMENDATIONS ................................................................. 6

A.1 Project GANTT Chart ............................................................................................. Error! Bookmark not defined.

A.2 Project target dates ............................................................................................... Error! Bookmark not defined.

A.3 Experimentation GANTT chart .......................................................................... Error! Bookmark not defined.

A.4 Experimentation target dates ............................................................................ Error! Bookmark not defined.

ANNEX B: DECLARATION ON PLAGIARISM ...................... ERROR! BOOKMARK NOT DEFINED.

ANNEX C: RESULTS ......................................................... ERROR! BOOKMARK NOT DEFINED.

2.1 Waste electric and electronic management

2.1.1 Waste management in South Africa

2.2 Chemical analysis and pre-treatment of printed circuit boards

2.3 Current processing strategies

2.4 Hydrometallurgical route

2.4.1 Sulfuric acid leach

Cu + Fe2(SO4)3(ag) ⇌ CuSO4(aq) + 2FeSO4(aq) (1)

Cu + 0.5O2(g) + H2SO4(aq) ⇌ CuSO4 + H2O (2)

Cu + H2O2 + H2SO4(aq) ⇌ CuSO4 + 2H2O (3)

2.4.2 Chloride leach of palladium, gold and silver

Pd + 2/3HNO3 + 4Cl− + 2H+ ⇌ PdCl42− + 2/3NO + 4/3H2O (4)

Pd + H2O2 + 4Cl− + 2H+ ⇌ PdCl42− + 2H2O (5)

Ag+ + Cl− ⇌ AgCl (6)

2.4.3 Thiourea leach

Au + 2NH2CSNH2 + Fe3+ ⇌ [Au(NH2CSNH2)2]+ + Fe2+ (7)

3. Conclusions and recommendations

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