You are on page 1of 11

REWAS 2008

Dr. B. Mishra, Dr. C. Ludwig, and Dr. S. Das


TMS (The Minerals, Metals & Materials Society), 2008

THE ROLE OF TOP SUBMERGED LANCE (TSL) TECHNOLOGY IN


RECYCLING AND CLOSING THE MATERIAL LOOP

Robert Matusewicz and Markus A. Reuter

Ausmelt Ltd, 12 Kitchen Road, 3175 Dandenong, Australia.


Keywords: Ausmelt Technology, Recycling, E-waste, Zinc and Lead, Spent pot lining
Abstract

Consumer products are a complex man-made mixture of sometimes in excess of 50 elements. In


order to recover these complex mixtures of elements either as metals, compounds or energy
requires versatile technology in physical separation but also smelting and energy recovery. This
paper explores this by referring to the innovative application of Top Submerged Lance (TSL)
technology and associated theoretical and environmental aspects to process (recycle) post
consumer materials and industrial intermediate products and residues. A diversity of applications
has been tested in Ausmelt’s pilot plant in Dandenong and many have gone to commercial scale
globally. This paper reviews the varied applications ranging from e-waste recycling, lead and
NiCd battery recycling, metals recovery from slags, zinc leach residue processing, electric arc
furnace (EAF) dust, Municipal Waste Incinerator bottom ash processing, carbon containing
residues such as retort ashes and spent pot liner from the aluminium production process as well
as use of the technology for materials such as automotive shredder residue (ASR) and plastics.

Introduction

The modern resource cycle is a link between primary production of metals linked to the
recycling of post-consumer goods. The sometimes complex combinations of materials and
metals in consumer products such as televisions depicted by Figure 1, does require a range of
technology to recover materials, metals and energy for reuse and/or recycling in an economically
feasible as well as environmentally friendly manner.

Figure 1. The interaction between primary and secondary metal production for use in consumer
products1,2.
951
Recyclates are never 100% pure; hence to recover for example the metals from these recyclates
in a metallurgical process requires a good control of the thermodynamics to ensure that the
metals report to the metal phase. Product design, collection, product distribution and physical
separation physics all affect the purity of recyclates and hence the recovery of the metals and
materials from post-consumer goods as depicted by Figure 2. It would be evident that
sophisticated and robust metallurgical technology is required to recover metals in such a
dynamic system in which consumer behaviour and legislation is constantly changing. Figures 1
and 2 reveal that the material cycle feeding consumer products is a web that connects product
design and consumer behaviour to mining, recycling and metal production. A common meeting
point of these interrelated activities is the smelting of metals in metallurgical furnaces.

Figure 2. The recycling chain of end-of-life products and the various actors and factors affecting
the efficiency of the recycling system2.

Top Submerged Lance (TSL) furnace technology provides a technology that meets many of the
requirements of closing the material cycle for non-ferrous metals shown in Figures 1 and 2
originating from diverse and varied feeds. Over more than 25 years Ausmelt
(www.ausmelt.com.au) has explored the many possible innovative uses of Top Submerged
Lance (TSL) technology to process ores, recycle post consumer materials and process industrial
intermediate products and residues. With over 47 industrial plants built, under construction or
design in 14 different applications, this has become one of the technologies of choice in the
nonferrous metallurgical industry and is also fast becoming the technology of choice for closing
the material cycle enabling energy recovery by processing post-consumer and industrial waste to
recover valuable metals and substituting primary fuels.

952
TSL Technology

There are many reasons why TSL technology can treat Cu, Zn, Pb, Sn, Ni, PGM containing ores
and various associated minor elements, industrial wastes and post-consumer materials and
products. These include the flexibility of the furnace to operate under various process
thermodynamic/kinetic conditions, the diverse feedstocks that it can treat, environmental
compliance with regard to plant emissions, the ability to produce slags that can be used as
building material, small physical footprint and of increasing importance, and its relatively low
carbon footprint.

A recent study commissioned by Ausmelt and performed by a reputed European company (PE
Europe, Stuttgart, Germany) that performs life cycle assessments, shows that TSL technology in
general compares with the best in the market not only with regard to CO2 emissions (Figure 3)
and other emissions such SOx, NOx and methane, which have been translated into indicators such
as Global Warming Potential (GWP), Photochemical Ozone Creation Potential (POCP), Abiotic
Depletion Potential (ADP) and Eutrophication Potential (EP). Hence TSL is paving the way not
only to make metal production more efficient, it is also lowering the carbon footprint of the
metallurgical industry in general. Ausmelt also is the only mainstream non-ferrous technology
supplier that can bring such benefits to the diverse range of recycle materials and industrial
wastes which are becoming increasingly important as resources due to example minor element
scarcity and hence their recovery from secondary resources, environmental legislation increasing
landfill costs as well as the carbon footprint of the metallurgical industry and its associated
carbon tax. With large applications of TSL as reflected by Table I in the appendix in which over
a million tonnes of concentrate are treated, these values will decrease a leave the industry more
environmentally friendly.

14.00

12.00

10.00
kg CO2/kg Blister Cu

8.00

6.00

4.00

2.00 Mitsubishi
Technology

Isasmelt
0.00
type

Ausmelt
Australia
Belgium Outokumpu
China
Finland
Country (Energy mix) USA

Figure 3. CO2 emissions as a function of technology and (possible) location in the five countries
with their respective energy mix reflecting different operating philosophies i.e. oxygen
enrichment, fuel usages (among others)3.

953
e-Waste Recycling

It is well known1,2 that recycling does contribute significantly in reducing the carbon footprint of
the metallurgical industry as well as society. Figure 4 shows how the elements in e-waste are
recovered in a single TSL reactor in which the thermodynamic properties are well controlled to
suite the two stages of the smelting operation. Recovering all valuable elements from e-waste
requires a sophisticated mix of neutral, oxidative and reductive steps in a defined sequence of
different stages within a single TSL reactor as shown in Figure 4. Using copper/lead as solvents
for valuable elements during the various steps facilitates the recovery of the metals. This is made
possible by the good metallurgical control possible to split the metals in the e-waste into the
required phases or into energy/steam.

Figure 4. Post-consumer e-waste treated in TSL technology with first neutral/oxidation and then
reduction steps within the TSL (also first reduction followed by oxidation is possible)

From Table 1 in the Appendix it is clear that we have been involved in numerous copper
processing plants both for primary metal production from concentrates as well as from secondary
copper sources. The secondary copper feed types do not only include copper containing scrap,
but would include the valuable copper containing parts of mobile phones, IT equipment,
televisions, as shown in Figure 1, but also using organic fractions which are part of the
motherboards and other plastic fractions as secondary fuels to lower the carbon footprint of the
process, with obvious economic benefits.

The preferred slag system implemented in the Ausmelt TSL reactor (depicted by Figure 4) for
smelting, reduction and (continuous) converting is an olivine type slag as depicted by Figure 5.
This figure shows the area at which the slag is molten. For example we are the only technology

954
supplier that uses this type of slag for continuous copper converting (C3), while Mitsubishi,
IsaConvert, continuous flash converting (Outokumpu) use calcium ferrite type slags. The use of
olivine has recently demonstrated successfully on industrial scale the applicability of using an
olivine type slag for continuous converting.

FCS
FS

FC

Figure 5. The FCS – Field or olivine type slag – the basis of all Ausmelt’s smelting processing,
where FS are iron-silicate (fayalite) and FC are calcium ferrite slags systems4.

Zinc Processing

More than 80% of the world’s annual 10.1 million tonnes of zinc production5 is via a process
path shown in Figure 6, which generates some 12 million tonnes of waste residue material6. At
its Whyalla Resource Recovery Facility Ausmelt treats such wastes, which in addition to
containing up to 22% zinc and 6% lead, is also environmentally less acceptable and occupies
large volumes.

In the present economic climate such wastes are increasingly being considered as a valuable
resource of various metals (both commodity and valuable minor) that could be recovered and
opens the door for the recovery of important metals such as Indium from electronic end-of-life
consumer goods. These zinc process wastes, known as jarosite, goethite, hematite and primary
leach residues, are typically stored in large dumps and few commercial processes are available
which provide a solution to this problem. Of the current paths available for treatment of these
waste residues, most are simply methods for reducing the volume of the residue produced and
still require construction of storage facilities like ponds or dams. Some processes attempt to
“fix” the waste residue7,8 in an effort to stabilise it and prevent leaching of toxic metals once
dumped. Some high temperature options are also available; however these sometimes also have
secondary environmental issues, therefore these do not really solve the environmental problem
but rather offer quick end-of-pipe fixes. Detailed analytical analysis of the proposal in the past
955
did show that processing these wastes with high temperature processes is the most advisable
route to follow9.

The Roast, Leach, Electrowin


Process for Zinc Production
Zinc Concentrate

Roasting Acid

Electrolysis Neutral Leach


Primary Leach
Residue
( Fe2O3)
Zinc Metal ~0.2 t/t Zn
20+% Zn
Further Leach

Jarosite Hematite Goethite


x[ Fe3(SO4)2(OH)6] or
( Fe2O3) or
(FeOOH )
~0.9 t/t Zn ~0.2 t/t Zn ~0.5 t/t Zn
3% Zn 1% Zn 6% Zn

Figure 6. 80% of world zinc production involves a process route that produces large amounts of
waste, which can be converted to a valuable resource with the aid of Ausmelt’s technology6,9.

A key ongoing development for TSL (driven by Korea Zinc) is to be able to treat these various
materials, requiring an ever more sophisticated process control model that will narrowly control
the slag chemistry window so that conditions are optimally monitored to ensure maximal zinc
fuming for example as depicted by Figure 7. Any change in the conditions can immediately
effect the operation by affecting the partial oxygen pressure, slag chemistry, liquidus
temperature, precipitated phases within the slag etc. Moving outside these boundaries due to the
change of feed to a TSL plant (which affects the composition within the reactor, the temperature
etc), will affect the product quality, therefore impacting ultimately on the carbon-footprint of the
process.

Various commercial applications of TSL technology by Ausmelt clients have been realized to
process zinc containing materials as discussed by Hughes et al. (2007)10 and Hughes et al.
(2008)11. Furthermore, we are using our own TSL technology to treat these zinc production
wastes in a staged (batch) process, processing some 55,000 t/a zinc residue in Whyalla. It is the
intention to transform this operation to one that operates continuously rather than in batch mode
to improve the throughput and hence also improve the economics of the process further.

956
D:\_MarkusR\2008\Ausmelt\PhaseDigrams\Bulgaria_Lime_1150_10_01ZnO.wmf

SiO2 - FeO - PbO - ZnO - CaO - O2


4/04/2008

o -10
1150 C, p(O2) = 10 atm, mass ZnO/Z = 0.1,
mass CaO/Z = 0.05, Z=(SiO2+FeO+PbO)
SiO2

.9 0.
0 1

1150oC 0
.8 0.
2

.7 0.
0 3

Slag + S(s4)

.6 0.
0 4

5 0.
0. Slag + S(s4) + Pb-liq 5

.4 Slag 0.
0 6

Slag + Olivine2
.3 Slag + Pb-liq 0.
0 7
AMonoxide + Slag + Olivine2

AMonoxide + Slag
.2 AMonoxide + Slag + Pb-liq 0.
0 8
Willemite + Slag + Pb-liq

1 0. D:\_MarkusR\2008\Ausmelt\PhaseDigrams\Bulgaria_Lime_1250.wmf
0. 9

SiO2 - FeO - PbO - ZnO - CaO - O2


4/04/2008

o -10
1250 C, p(O2) = 10 atm, mass ZnO/Z = 0.05,
mass CaO/Z = 0.05, Z=(SiO2+FeO+PbO)
PbO FeO
0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1

mass fractions /(SiO2+FeO+PbO) SiO2

9 0.
0. 1

8 0.
0. 2

7 0.
0. 3

1250oC
Slag + S(s4)

6 0.
0. 4

5 Slag + S(s4) + Pb-liq 0.


0. 5

4 0.
0. Slag 6

3 0.
0. 7
Slag + Pb-liq

2 0.
0. 8

1 0.
0. 9
AMonoxide + Slag + Pb-liq

PbO FeO
0.9 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1

mass fractions /(SiO2+FeO+PbO)

Figure 7. An example of the effect of temperature on the slag chemistry area of interest. A low
temperature results in operation outside of the desired (shaded) region i.e. totally molten slag.

Lead battery and residue recycling

Table I in the appendix summarizes various recent commercial and new lead smelting projects.
The present boom in the metals industry has been instrumental in the large number of contracts
awarded to Ausmelt. Notable amongst these have been the numerous contracts for the processing
of lead ores and post consumer lead materials, such as batteries, with plants being constructed in
Bulgaria, Brazil, China and Russia.

The first recycling plant for lead residue materials went into operation in 1996 in Nordenham,
Germany (now Weser Metall)12.

BATTERY BREAKER FEED SYSTEM FURNACE BUILDING OFFGAS SYSTEM SULPHUR CAPTURE

BATTERY + - FEED DELIVERY GAS COOLING


+ -
COLLECTION
Bag House

BATTERY
BREAKING
Stack
Jaw Crusher ID Fan
SO2 Scrubber

Evaporative Gas
BULK STORAGE
Battery Grids DAY STORAGE Molten Discard Cooler
Classifier Battery Paste Slag Crude Bullion
Halide
Washing

Spent Acid to
Recycle Slag Pb Dust to Recycle
AUSMELT®
Granulated TSL FURNACE DUST HANDLING
Discard Slag Slag Granulation

GRANULATION
Refined Bullion

Ingot Casting
Electricity Water Air Transport Saftey
Refining

SERVICES REFINERY
 
Figure 8. A schematic of a typical TSL type operation for Pb-Battery recycling.

957
A further application of this is the recently signed contract with Votorantim that will treat lead
concentrates, lead-bearing residues, battery scrap and specified recycles sufficient to produce
75,000 tonnes per annum of refined lead. A single Ausmelt furnace will be used to conduct a two
stage (Smelt and Reduction) batch process. This plant is due for start-up mid to late 2009, with a
process schematic depicted in Figure 9. A simple indication of the slag chemistry to realize this
is depicted by Figure 7.
• Lead Concentrates • Lead Residues
• Battery Scrap • Refinery Reverts
• Fluxes Air, Fuel & Oxygen

Solids

Venturi
Scrubber
Smelting
Stage
Removal of Liquid
unwanted Solution Fume /
elements Dust

Slag
Reductant Coal
Air, Fuel &
Oxygen

Lead Bullion
to Refinery

Fume / Slag Reduction


Dust
Stage

All stages are


F1
completed within a
single Ausmelt
Tapped Slag
Furnace

Figure 9. Process flowsheet for Votorantim Metais.

Some special Ausmelt applications

Figure 7 shows that changing the metallurgical process conditions within a TSL produce
different outcomes. Without going into the depth of the theory and operating conditions possible
within a TSL, the versatility and range of thermodynamic, kinetic as well as flow conditions
achievable in TSL is best illustrated by the following examples. These show that diverse and
changing post-consumer materials and industrial environmental issues/problems can be solved
economically (as these applications are/were industrial reality), in the process producing benign
slags for construction type applications, metals can be recovered both into metal phase and into
the flue dust from these feed types.

Bottom ash treatment from waste incinerator

During the waste-to-energy processing of municipal waste, a bottom ash is created. An Ausmelt
plant has been built in integrated into the Waste-to-Energy operation at the Municipal Mapo
Resource Recovery Plant in Seoul, South Korea. The benign slag product produced by the
Ausmelt furnace is processed into bricks and used in pavements, gardens, etc. This unique

958
application reduces the mass of municipal household waste to less than 1%, the final residue that
has to be landfilled.

Spent pot lining (SPL) treatment from aluminium industry

Spent pot lining (SPL) is a hazardous waste material of the aluminium industry. In an unique
application the SPL is processed in an Ausmelt furnace (Table 1) to produce a benign slag and
AlF3 fed back to the aluminium smelter while using the carbon as the fuel to the process.

NiCd-battery recycling

Ausmelt successfully conducted pilot scale trials to process discard NiCd batteries from mobile
phones and other sources. These trials were successful in producing saleable nickel and cadmium
products.

Design for Recycling: EAF dust and shredder residue

Figure 2 gives an overview of automotive recycling. Design for Recycling models can for
example calculate the recyclablity of cars, both old as well directly during the design phase2.
These models predict the quality of various recyclates produced during physical separation as a
function of design. These recyclates are now partially being treated economically, but certain
fractions still end in landfill. Whereas TSL can treat EAF dust without any problems, shredder
fluff is an interesting residue which is easily treatable in a TSL, utilizing both its organic content
as fuel and carbon source for reduction to recover the contained metals, glass, sand, etc. into a
slag and into a metal phase if the conditions are created for doing this.

These industrial as well as pilot scale applications do reflect that the full potential of TSL
technology has not been reached. We will continue to drive such applications in the coming
years to industrial applications and further establish TSL technology as the technology of choice.
This work is being supported by various focussed R&D and industrial projects to lower the
carbon footprint of the technology even more.

References

1. M.A. Reuter et al. (2005): The Metrics of Material and Metal Ecology, Harmonizing the
resource, technology and environmental cycles Elsevier Science, Amsterdam, 706p. 2005
(ISBN: 13 978-0-444-51137-9).
2. M.A. Reuter and A. van Schaik (2008): Thermodynamic Metrics for Measuring the
“Sustainability” of Design for Recycling, Journal of Metals, Vol. 60(8), pp. 39-48.
3. M.A. Reuter and R. Matusewicz (2008): Ausmelt’s TSL technology: Innovating in energy
efficient metal production, recycling and waste processing, The AusIMM Bulletin,
March/April, pp. 12-13.
4. R. Matusewicz, S. Hughes, and J. Hoang (2008): The Ausmelt Continuous Copper
Converting (C3) Process, In proceedings Cu2007, The Carlos Diaz Symposium on
Pyrometallurgy, (Ed. A.E.M. Warner, C.J. Newman, A. Vahed, D.B. George, P.J. Mackey,
A. Warczok), Met Soc of CIM, Vol. 3(2), pp. 29-47.

959
5. Y. Umetsu (2005): Advances and Challenges in Zinc Production, Proceeding of the
International Symposium on Lead and Zinc Processing, Kyoto, Japan, October 17th-19th,
2005, p. 89.
6. M.A. Reuter et al. International Zinc Association, Zinc College Course Notes, 2001/2003,
p.117. (ISBN 90-805644-5-1)
7. S. Sylvain, T. T. Chen, J. Dutrizac (2001): Jarofix: Addressing Iron Disposal in the Zinc
Industry, Journal of Metals, Vol. 53(12), pp. 32-34.
8. C. Geenan, R.A. Maamar, C. Eusebe (2005): Main Developments in Umicore Zinc Smelting,
Proceeding of the International Symposium on Lead and Zinc Processing, Kyoto, Japan,
October 17-19, 2005, pp. 247ff.
9. S. Sudhölter, M.A. Reuter and J. Krüger (1996): Eco-techno-economic synthesis of process
routes for the production of zinc using combinatorial optimisation, Metallurgical
Transactions B, Vol. 27B(6), pp. 1031-1044.
10. S. Hughes, R. Matusewicz, M.A. Reuter and D. Sherrington (2007): Extracting value from
EAF Dust, Proceedings EMC 2007, Vol. 3 (Zinc and Lead, Light Metals and General
Hydrometallurgy), GDMB, Clausthal, Germany, pp. 1993-1208.
11. S. Hughes, M.A. Reuter, R. Baxter and A. Kaye (2008): Ausmelt technology for lead and
zinc processing, In Proceedings Lead and Zinc 2008, 25-29 February 2008 (Ed. W. van der
Merwe), South African Institute of Mining and Metallurgy (SAIMM), South Africa, pp. 147-
162 (ISBN: 978-1-920211-12-7).
12. J. Manthey (2008): Moderne Bleierzeugung: ein Vergleich zum alten Schachtofenbetrieb,
NE-Metall-Recycling – Grundlagen und aktuelle Entwicklung, 43. Metallurgischen Seminar
der GDMB, 9-11 April 2008, Dortmund, Germany pp. 145-152.

960
Appendix

Table I: List of recent Ausmelt TSL plants reflecting the location, type of material processed,
size of the plants, which plants have already been commissioned and which are being presently
constructed/designed.
Client Location Starting Feed type Annual Product Furnace Temperature Fuel
year throughput ID range (°C)
(t/y) (m)

Undisclosed Asia 2011 Cu Secondaries 110,000 Cu Metal Under 1150-1200 TBA


Design

Empresa Bolivia 2010 Sn concentrates 38,000 Sn Metal Under 1150-1200 Natural Gas
Metalurgica Design
Vinto

Undisclosed China 2010 Cu Concentrates 1,250,000 Cu Matte Under 1200 Coal


Design

Undisclosed China 2010 Cu Concentrates 450,000 Cu Matte Under 1200 Coal


(F1) Design
(2 Ausmelt
furnaces) 2010 Cu Matte 190,000 Blister Cu Under 1250 Coal
(F2) Design

Intertrust Kurdjali, 2010 Pb Concentrates / 125,000 Pb Bullion Under 1150-1250 Coal


Bulgaria Battery Scrap/Lead Design
Slag

Votorantim Juiz de Fora, 2009 Pb Concentrates/ 175,000 Pb Bullion 4.0 1150-1250 Natural Gas
Metais Brazil Battery Scrap

Undisclosed Former 2009 Pb Concentrates 71,000 Pb Bullion 2.5 1070-1100 HFO


Soviet Union

Young Sukpo, South 2008 Pb Residues 120,000 Pb Fume Under 1250 Coal
Poong Corp. Korea (F1) Design
(2 Ausmelt 2008 F1 Slag (liquid) 100,000 Pb/Zn Fume Under 1300 Coal
furnaces) (F2) Design

Yunnan Tin Gejiu City, 2008 Pb Concentrates 190,000 Pb Bullion Under 1150-1250 Coal
Corporation China Design

Chifeng Chifeng, 2008 Cu Concentrates 480,000 Cu Matte 4 1200 Coal


Jinjian Inner
Copper Mongolia,
Group China

Huludao Huludao, 2008 Cu Concentrates 500,000 Cu Matte 4.4 1180 LFO/zinc


Copper China retort
Group

Jilin Nickel Jilin 2008 Ni/Cu Concentrates 275,000 Ni/Cu Matte 3.6 1350 LFO/coal
Group Province,
China

Jinchuan Gansu 2008 Ni/Cu Concentrates >1 million Ni/Cu Matte 5 1350 Coal
Nonferrous Province,
Metals Corp. China

Ausmelt Whyalla, 2008 Zn Leach Residues 55,000 Zn Fume 5x3 1300-1350 Coal
Australia (elliptical)

Korea Zinc Onsan, South 2007 Zn Leach Residues 120,000 Zn Fume 3.9 1300 Coal
Korea (F1)
(2 Ausmelt
furnaces) 2007 F1 Slag (liquid) 100,000 Zn fume 3.9 1350 Coal
(F2)

Dowa Akita, Japan 2007 Cu Secondaries 150,000 Cu Metal 4.0 TBA TBA
Mining Co.
Ltd.

961