Part 3 - Processing of Urban Ores

Extractive Metallurgy
Part 4 Processing of Urban

Ores
A/Prof Akbar Rhamdhani
Department of Mechanical and
Product Design Engineering
Universitas Indonesia
23 November 4 December 2015
CRICOS Provider
00111D
What should you hope to gain?
Swinburne
An understanding of what is E-waste or WEEE (Waste of

Electronics and Electrical Equipments)
An understanding of the processing routes and metals
recovery from E-waste
An understanding of challenges in the optimisation of ewaste processing
SCIENCE | TECHNOLOGY | INNOVATION | BUSINESS | DESIGN
References
Swinburne
Khaliq, A., Rhamdhani, M.A., Brooks, G.A. and Masood, S., "Metal Extraction
Processes for Electronic Waste and Existing Industrial Routes: A Review and
Australian Perspective", Resources (Special Issue - Wealth from Waste: Urban Metal
Resources and Industrial Ecology), 3(1), 2014, 152-179
Rhamdhani, M.A., Khaliq, A., Brooks, G.A., Masood, S., Ahmad, S., Islam, M.S., "More
from Less, Generating Wealth from Lower Grade and Urban Metal/Ore Sources",
Advanced Materials Research, vol.112, 2015, pp.481-484.
Cui, J. and L. Zhang, Metallurgical recovery of metals from electronic waste: A review.
Journal of Hazardous Materials, 2008. 158(2-3): p. 228-256.
Park, Y.J. and D.J. Fray, Recovery of high purity precious metals from printed circuit
boards. Journal of Hazardous Materials, 2009. 164(23): p. 1152-1158
Reuter, M. A., Hudson, C., van Schaik, A., Heiskanen, K., Meskers, C., Hagelken, C.,
UNEP (2013) Metal Recycling: Opportunities, Limits, Infrastructure, A Report of the
Working Group on the Global Metal Flows to the International Resource Panel, 2013.
Declining Metal Ore Grade Worldwide
Swinburne
UNEP. Recycling
Rates of Metals A
status report, A report
of the Working Group
on the Global Metal
Flows to the
International Resource
Panel, T.E. Graedel, et
al. (2011)
Declining Metal Ore Grade Worldwide
Swinburne
Northey et al 2014
Driving force
Lowering of the grade of ores around the world
Availability of alternative resources for metals
o Low grade/weathered ores
o
Weathered ores (ilmenite, laterite, etc)
o Urban ores
o
Industrial Waste
Electronic Waste (E-Waste, WEEE)
Other driving force

o Environmental concerns
o Energy and Resource Conservation
o Economic values
Swinburne
What is E-Waste
Swinburne
European WEEE Directive

Electrical or electronic equipment which is waste including all components,
sub-assemblies and consumables, which are part of the product at the time of
discarding. [2, 3].
Basel Action Network

E-waste encompasses a broad and growing range of electronic devices
ranging from large household devices such as refrigerators, air conditioners, cell
phones, personal stereos, and consumers electronics to computers which have
been discarded by their users.[4]
Swinburne
What is E-Waste
Electronic Waste
20-25 million tonnes are generated annually (global)
Great challenges and also opportunities
Contain:
Precious Metals:
Au, Ag
Platinum Group Metals:
Pd, Pt, Rh, Ir and Ru
Base Metals:
Cu, Al, Ni, Sn, Zn and Fe
Hazardous Elements:
Hg, Be, In, Pb, Cd, As and Sb
Scarce Elements:
Te, Ga, Se, Ta and Ge
Swinburne
What is E-Waste
Table 1: WEEE/e-waste categories according to the European directive on WEEE [2, 3]
No Category
Label
Large household appliances
Large HH
Small household appliances
Small HH
IT and telecommunications equipment
ICT
Consumer equipment
CE
Lighting equipment
Lighting
Electrical and electronic tools (with the exceptions of largescale stationary industrial tools)
E & E tools
Toys, leisure and sport equipment
Toys
Medical devices (with the exception of all implanted and

infected products)
Medical
equipment
Monitoring and control instruments
M&C
10
Automatic dispensers
Dispensers
Swinburne
What is E-Waste
Weight versus value distribution in E-Waste
Fe
Al
Cu
Plastics
Ag
Au
Pd
TV-board
PC-board
(wt %)
28%
7%
(wt %)
10%
5%
(wt %)
10%
20%
(wt %)
28%
23%
(ppm)
280
1000
(ppm)
20
250
(ppm)
10
110
Mobile phone
5%
1%
13%
56%
1380
350
210
Portable audio
23%
1%
21%
47%
150
10
DVD-player
Calculator
62%
4%
2%
5%
5%
3%
24%
61%
115
260
15
50
4
5
Value-share
Fe
Al
Cu
Sum Precious
Metals
Ag
Au
Pd
TV-board
PC-board
4%
0%
11%
1%
42%
14%
43%
85%
8%
5%
27%
65%
8%
15%
Mobile phone
0%
0%
7%
93%
5%
67%
21%
Portable audio
3%
1%
77%
19%
4%
13%
2%
DVD-player
Calculator
13%
0%
4%
5%
36%
11%
47%
84%
5%
7%
37%
73%
5%
4%
Weights %
Swinburne
E-Waste
10 kg
Containing 2g Au
1,000 kg
200g (Au)
100 kg (Cu)
500 kg to 1,000 kg
3 kg (Ag)
100 g (Pd)
Metals in PCB
Swinburne
Table 11: Examples of composition of mobile phones, PCs and

laptops and the impact on metal demand based on 2010 sales
(UNEP, 2009; Hageluken and Corti, 2010).
Characteristics of E-Waste
Swinburne
Complex microstructures
o Contain remarkably different components, e.g. plastics
(hydrocarbons), glass (oxides), metals (ferrous and non-ferrous),
and other components
Complex compositions
o The metals of interests are usually in minor proportion (very low
concentration)
o They contain large number of elements (including valuable and
hazardous substances), e.g. more than 40 metals on a cell phone
o Varies for different locations, products, and time
Increased Materials Complexity
Swinburne
UNEP. Metal Recycling

Opportunities, Limits, Infrastructure,
M. Reuters, et al. (2014)
Recoverability of Metals
Swinburne
Table 1 Compatibility matrix as a
function of metallurgical recovery (van
Schaik and Reuter, 2012; Reuter and
van Schaik, 2012a&b) (PMs: precious
metals; PGMs: platinum group metals).

General Steps in Processing of E-Waste
Swinburne
Collection
-
Government policies
Public awareness
Easy access to collection facilities
Pre-processing
-
Using similar method used in physical processing of ores

Sorting and dismantling (manual vs automatic)
Materials liberation (housing, wiring boards, drives)
Mechanical processing (shredder, hammer mills)
Separation of metals and non-metals (screening, magnetic, eddy
current, density separation)
End-processing
-
Further processing of non-metal and metal fractions

Metallurgical processes to recover metals
Pre-Processing of E-Waste
Swinburne
Go to End-processing
The pre-processing of e-waste to separate metal
and non-metal fractions
Swinburne
Particle size vs specific energy of treatment of PCB
Laurmaa et al. TMS 2011

Swinburne
Effect of the complexity of materials on liberation

Swinburne
Trade off recovery grade vs recovery rate

Physical Separation Processes
Swinburne
Sensor-based sorter

Swinburne
Eddy Current separator

Swinburne
Rising-Current separator

Swinburne
Hydrocyclone separator
UNEP. Metal Recycling Opportunities, Limits, Infrastructure, M.

Reuters, et al. (2014)
Metallurgical Processes to Recover Metals

from E-Waste
Swinburne
Hydrometallurgical routes
Pyrometallurgical routes
Pre-processing and leaching

using acid/caustic solutions
Separation of precious metals
from leachants using solvent
extraction, adsorption, and ion
exchange methods
Metals extraction processes are
similar to mineral processing
Pre-processing is not necessary

for small devices
Direct feeding into furnace at
high temperature
Metal fraction end up in molten
bath
Plastics partially replace coke
and act as reducing agent and
fuel
Oxides end up in slag phase
Heat Values of Different Plastics
Zuo and Zhang, TMS 2011
Swinburne

from E-Waste
Hydrometallurgy Route
Swinburne
- HNO3, H2SO4, HCl based solutions are commonly

employed for dissolving precious metals from e-waste
- From the leachants, precious metals are recovered
employing methods similar to that are being exercised in
mineral industry
- Complex electrolyte solutions that have to be purified
before metals can be produced
- Creates complex sludges and residues that must be dealt

with in an environmentally sound manner

from E-Waste
Recovery of precious metals from leachate
Swinburne
- Cementation
-
Merill-Crowe process: cathodic deposition of gold and anodic

corrosion of zinc, which occur at the surface of zinc particles
- Solvent extraction
- Activated carbon
- Ion exchange

from E-Waste
Example of hydrometallurgical
recycling of PCBs for the recovery of
precious metals [Park and Fray]
Swinburne

from E-Waste
Swinburne
Investigators
Leaching agent
Process conditions
Recovered metals
Park and Fray

[41]
Aqua regia
Ratio of metals to leachant = 1:20 g/ml
Au, Ag, Pd
Extraction was carried out in three stages (Self

agitation)
Au
HNO3 (1st stage), Epoxy

Sheng and Estell
resin (2nd stage), Aqua
[50]
regia (3rd stage)
Quinet et al [51]
Chielewski et al
[52]
Zhou et al [53]
Kogan [54]
Veit et al [11]
Mecucci and
Scott [55]
Leaching & metals recovery by cementation,

H2SO4, Chloride, thiourea,
precipitation, ion exchange and carbon
cyanide leaching
adsorption
Au, Ag, Pd, Cu
Roasting of E-waste in the presence of carbon

Leaching with HNO3 and aqua regia
Solvent extraction with diethyle malonate
Au
NaClO3
Combustion of E-waste at 400-500oC followed

by leaching.
Ag, Au, Pd
HCl, MgCl2, H2SO4
Dissolution of E-waste in different solvents and

conditions
H2O2
Recovery of metals in stages
HNO3
Aqua regia
HCl, H2SO4
Aqua regia
Al, Sn, Pb and Zn (1st

stage), Cu and Ni (2nd
stage), Au, Ag, Pd and
Pt (last stage)
H2SO4
Mechanical processing and then dissolution of eCu

waste in different solvents
HNO3
Electrochemical deposition of Cu at cathode

from solution
Pb, Cu
SCIENCE
| TECHNOLOGY
| INNOVATION | BUSINESS
| DESIGN of precious metals from e-waste (Khaliq et al 2014)
Table
7: Summary
of hydrometallurgical
recovery

from E-Waste
Limitations of Hydrometallurgy Route
Swinburne
In general slow and time consuming impact on recycling economy
Longer mechanical pre-processing of e-waste to reduce size for

efficient dissolution. 20% precious metal could be lost during
liberation process
Problems associated with leachant

- cyanide hazardous, environmentally unfriendly
- halide corrosive and oxidizing
- thiourea high cost and consumption
- thiosulfate high consumption
There are possibilities of precious metals loss during dissolution and

subsequent steps, therefore the overall recovery of metals will be
affected

from E-Waste
Pyrorometallurgy Route
Swinburne
The use of high temperature to process E-waste
Smelting in furnaces, incineration, combustion and pyrolysis
Liberation, separation/upgrading and purification are carried out by

exploiting metals chemical and metallurgical properties, e.g. precious
metals are segregated into copper or lead make a precious
metals concentrate using metal carrier
Currently, copper and lead smelters work as e-waste recyclers for the
recovery of Pb, Cu and precious metals
Understanding of thermodynamics and process metallurgy are

required to optimize process
Metal Wheel
Swinburne
Reuter and van Schaik (2012a, 2012b)

from E-Waste
Lead Smelting Route
Swinburne
Sulfide ores sintering, reduction and refining
Sintering pyrite, lime rock, silica and high concentrated lead
Reduction in blast furnace with the help of coke molten lead

with about 85% purity
Refining stage
-
copper dross is skimmed off from the lead dross and is treated in a
reverberatory furnace
lead dross is processed by adding wood chips, fine coke and sulfur
lead bullion (rich in lead), matte (copper and other metals sulfides) and
speiss (high in arsenic and antimony contents)
Matte and speiss are treated in copper smelters for the extraction of
copper and other associated metals
precious metals are separated from lead bullion by Parkes process, in
which zinc forms insoluble intermetallic with gold and silver

from E-Waste
Copper Smelting Route
Swinburne
Primary Copper Production Route

- Sulphide ores processed to produce copper matte (40%Cu) then
to blister copper (98.5%). Finally, blister copper is refined by fire
refining and electrorefining to produce pure copper
Secondary Copper Production Route

- e.g. the black copper route
- consists of reduction and oxidation cycles
- followed by refining in anode furnace and electrorefining to
produce pure copper
The precious metals go with the copper, and segregated into anode
slime after the electrorefining and further processes for recovery
E-Waste processing embedded in

primary Cu production
Swinburne
The flow of elements associated with copper production (hydro- and pyro-metallurgy) showing the link
between primary production and recycling. (Nakajima et al., 2008; 2009; 2011; Nakamura and Nakajima,
2005; Nakamura et al., 2007).
Swinburne
E-Waste processing embedded in

secondary Cu production
Black Copper Smelting Route
Metal
Metal Scrap,
Scrap, E-waste
E-waste
Oxide
Oxide Feed,
Feed, Coke,
Coke, Fluxes
Fluxes
Copper
Copper Scrap
Scrap
Black
Black
Copper
Copper
Slag
Slag to
to Waste
Waste
Reduction
Blister
Blister
Copper
Copper
Oxidation
Anode
Anode Copper
Copper
Electrorefining
Anode
Furnace
````
Slag
Slag
Cooler
Baghouse
Zinc
Zinc Rich
Rich Fume
Fume
Cooler
Cooler
Baghouse
Baghouse
Zinc-Tin-Lead
Zinc-Tin-Lead Fume
Fume
Cooler
Baghouse
Copper-Zinc-Lead
Copper-Zinc-Lead Fume
Fume
Anode
Sludge
Precious
Metals
Copper
Copper
Cathode
Cathode
Industrial Processes for Recovery of

Metals from E-Waste
Copper Smelting Route
-
Umicore integrate smelting and refining facility, Belgium
Noranda process in Quebec, Canada
Rnnskr smelters in Sweden
Kosaka recycling plant in Japan
Kayser recycling system KRS in Austria and Germany
Metallo-Chimique N.V plants in Belgium and Spain
Swinburne
Integrated Smelting and Refining
Swinburne
Noranda smelting (Cu

concentrate and e-waste
is fed into furnace at
1250oC), Veldbuizen and
Sippel (1994).
Swinburne
A flowsheet for Umicores integrated metals

smelter and refinery, Hageluken (2006)
Aerial view of Umicore plant at

Hoboken/Antwerp, Hageluken and Corti (2010)
Swinburne
A Korean Zinc flowsheet plant to recover valuable elements associated with zinc minerals, such as
indium, which are critical to flatpanel TV technology (Hoang et al., 2009).
Swinburne
The Kayser Recycling System for recycling copper metal and other copper containing residues

Flow sheet diagram of Rnnskr Smelter, Sweden
Swinburne
Swinburne
Summary of selected pyrometallurgical methods for recovery of metals from e-waste

Industrial processes
Metals recovered
Umicores process
Au, Ag, Pd, Pt, Se, Ir, Ru, Rh,
[20, 63, 64]
Cu, Ni, Pb, In, Bi, Sn, As, Sb
Outotec TSL [68]
Zn, Cu, Au, Ag, In, Pb, Cd, Ge
Rnnskr smelters
[66, 69]
Noranda process [67]
Rnnskr smelters
[66, 70]
Umicores trials [71]
Dowa mining Kosaka
Japan [72]
LS-Nikko,s recycling
facility, Korea [73]
Main process features

IsaSmelt smelting, copper leaching & electrowinning and
precious metals refinery
Top submerged lanced furnace (Ausmelt TSL), Smelting of ewaste in copper/lead/zinc processes
Smelting in Kaldo reactor, upgrading in copper and followed by
Cu, Ag, Au, Pd, Ni, Se, Zn, Pb
refining, high precious metals recovery
Smelting of e-waste and Cu concentrate. Upgrading in
Cu, Au, Ag, Pt, Pd, Se, Te, Ni converter and anode furnaces. Electrorefining for metal
recovery
PC scrap feeding to Zn fuming process, Plastics is used as
Cu and precious metals
reducing agent, Precious metals are segregated in Cu and are
recovered at later stage
Au, Ag, Pd, Pt, Se, Ir, Ru, Rh,

Cu, Ni, Pb, In, Bi, Sn, As, Sb
Plastics from e-waste is tested at energy and reducing agent

during smelting
Cu, Au, Ag
E-waste smelting in copper flash converter
Au, Ag & PGMs metals
Recycling in TSL smelting followed by electrolytic refining
Days patent [74]
Precious metals, Pt and Pd
Aleksandrovich patent
[75]
PGMs and gold
Aurubis recycling
Germany [76]
Cu, Pb, Zn, Sn and PMs
Smelting in plasma arc furnace at 1400oC. Precious metals

collected in base metal. Ceramic residue went in the slag
phase. Ag and Cu used to collect metals during process
Scrap combustion in a base metal using carbon as reducing
agent, Solidification and separation of solidified product are
carried out by formed phase boundaries
Smelting of Cu and e-waste in TSL reactor, black copper
processing and finally electrorefining
Technical Challenges
Swinburne
Fundamental knowledge
o A limited fundamental knowledge about this new complex
materials and how to effectively process them
Thermodynamics, Kinetics, Separation, Refining, Extraction, and

Materials etc
Processing Technologies and Routes

o Extensive pre-processing and main extraction processes longer
overall process chains
o Development of new or modification of existing technologies and
processes
Systematic analyses of modified or new technologies and process

routes, in terms of techno-economic, impact to environment (e.g. life
cycle assessment), scale up from laboratory to full size plant, and
feasibility, need to be considered
Technical Challenges
Swinburne
A table of challenges in separation still required in WEEE recycling
Techno-economic of analysis of E-waste

processing embedded in Cu production
Swinburne

Swinburne

Swinburne
Effect of Production Scale on the Economic
Swinburne
Non-Technical Challenges
Swinburne
Overall economic of the process

o This often becomes the main driving force
o New and innovative business models may also need to be
developed to shift towards more economical process
Infrastructure and logistics

o Facilities for pre-processing, in addition to the main extraction
processes facilities
o A good collection system, e.g. the network of collection,
transportation of the resources and associated costs
o Consideration of the size of the facilities, from a small scale citybased to a large scale integrated smelting-recycling plants
Non-Technical Challenges
Swinburne
Government systems
o Governmental policies and legislation to promote and drive the
market for processing towards the alternative resources
o Provide a framework for the development of innovative business
models
o Government incentives
Social/socioeconomic challenges
o Education and information flow in the society about recycling
and underlying wealth associated with the above ground waste
o Different paradigms and cultures within the society that can act
as a barrier
Concluding Remarks
Swinburne
- E-waste is a complex material. It provides an alternative

resources for metals.
- The driving force for processing E-waste: lowering of
grade ores, environmental concerns, energy and resource
conservation, economic values.
- General steps in processing of e-waste include:
collection, pre-processing and end-processing
- Two general routes in recovering metals from E-waste are
through hydrometallurgy and pyrometallurgy
- In industry, combined pyrometallurgy and hydrometallurgy
routes is used
53
Concluding Remarks
Swinburne
- There are technical and non-technical challenges for a

sustainable processing of alternative resources that need
to be overcame
- A comprehensive approach addressing both of these
challenges needs to be applied
o Innovations in all sectors from science, technology, social,
governmental policy to business will be vital in promoting the
use of the alternative resources for maximized resource efficiency
and wealth generation
54
A/Prof Akbar Rhamdhani

ARhamdhani@swin.edu.au
Let us do more to maximise resource

efficiency for sustainable future
CRICOS Provider 00111D

Part 3 - Processing of Urban Ores

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Extractive Metallurgy

Part 4 Processing of Urban

What should you hope to gain?

An understanding of what is E-waste or WEEE (Waste of

An understanding of challenges in the optimisation of ewaste processing

SCIENCE | TECHNOLOGY | INNOVATION | BUSINESS | DESIGN

SCIENCE | TECHNOLOGY | INNOVATION | BUSINESS | DESIGN

Declining Metal Ore Grade Worldwide

SCIENCE | TECHNOLOGY | INNOVATION | BUSINESS | DESIGN

Declining Metal Ore Grade Worldwide

SCIENCE | TECHNOLOGY | INNOVATION | BUSINESS | DESIGN

Weathered ores (ilmenite, laterite, etc)

Electronic Waste (E-Waste, WEEE)

Other driving force

SCIENCE | TECHNOLOGY | INNOVATION | BUSINESS | DESIGN

European WEEE Directive

Basel Action Network

SCIENCE | TECHNOLOGY | INNOVATION | BUSINESS | DESIGN

Platinum Group Metals:

Pd, Pt, Rh, Ir and Ru

Cu, Al, Ni, Sn, Zn and Fe

Hg, Be, In, Pb, Cd, As and Sb

Te, Ga, Se, Ta and Ge

SCIENCE | TECHNOLOGY | INNOVATION | BUSINESS | DESIGN

Table 1: WEEE/e-waste categories according to the European directive on WEEE [2, 3]

Large household appliances

Small household appliances

IT and telecommunications equipment

Toys, leisure and sport equipment

Medical devices (with the exception of all implanted and

Monitoring and control instruments

SCIENCE | TECHNOLOGY | INNOVATION | BUSINESS | DESIGN

SCIENCE | TECHNOLOGY | INNOVATION | BUSINESS | DESIGN

SCIENCE | TECHNOLOGY | INNOVATION | BUSINESS | DESIGN

Table 11: Examples of composition of mobile phones, PCs and

SCIENCE | TECHNOLOGY | INNOVATION | BUSINESS | DESIGN

SCIENCE | TECHNOLOGY | INNOVATION | BUSINESS | DESIGN

Increased Materials Complexity

UNEP. Metal Recycling

SCIENCE | TECHNOLOGY | INNOVATION | BUSINESS | DESIGN

UNEP. Metal Recycling

General Steps in Processing of E-Waste

Using similar method used in physical processing of ores

Further processing of non-metal and metal fractions

SCIENCE | TECHNOLOGY | INNOVATION | BUSINESS | DESIGN

Particle size vs specific energy of treatment of PCB

Laurmaa et al. TMS 2011

UNEP. Metal Recycling

Trade off recovery grade vs recovery rate

UNEP. Metal Recycling

SCIENCE | TECHNOLOGY | INNOVATION | BUSINESS | DESIGN

Physical Separation Processes

SCIENCE | TECHNOLOGY | INNOVATION | BUSINESS | DESIGN

UNEP. Metal Recycling

Physical Separation Processes

Eddy Current separator

SCIENCE | TECHNOLOGY | INNOVATION | BUSINESS | DESIGN

UNEP. Metal Recycling

Physical Separation Processes

SCIENCE | TECHNOLOGY | INNOVATION | BUSINESS | DESIGN

UNEP. Metal Recycling

Physical Separation Processes

UNEP. Metal Recycling Opportunities, Limits, Infrastructure, M.

Metallurgical Processes to Recover Metals