Copper Recycling

ENGR5187 Solid Waste Processing and Recycling
(Term Paper)
Copper Recycling
Alberto Rui Frutuoso Barroso March 24, 2010 Laurentian University
ABSTRACT
This document provides a general description of how copper is produced from ore and scrap, and a more detailed synopsis of the equipment, processes and logistics of the copper recycling industry. A list of the latest technologies in smelting, converting, and melting furnaces is given, along with equipment capabilities in primary and secondary copper production. The current status of secondary copper production in the United States is compared to that of Canada and Europe, and the transference of primary and secondary copper processing for countries with the biggest growing economies in the world is referred. The techniques to recycle copper from general mechanical and electrical scrap are analyzed, and a special focus is given to the recycling methods of electronic equipments, because of the recent recycling pressure that these copper products receive due to an extremely ephemeral utilization rate.
II
Contents
1. INTRODUCTION ...............................................................................................................................................1 1.1 1.2 2. THE COPPER INDUSTRY ...........................................................................................................................1 COPPER PRODUCTION AND USAGE ..................................................................................................................2
METALLURGY OF COPPER ..........................................................................................................................4 2.1 INTRODUCTION ...............................................................................................................................................4 2.2 COPPER COMMINUTION ................................................................................................................................... 5 2.3 COPPER FROTH FLOTATION ............................................................................................................................. 5 2.4 FURNACES USED IN COPPER PRODUCTION ........................................................................................7 2.4.1 Outokumpu flash furnace .......................................................................................................................8 2.4.1 ValeInco flash furnace ...........................................................................................................................9 2.4.2 Noranda and El-Teniente bath smelting furnace ................................................................................. 10 2.4.3 AUSMELT and ISAMELT furnace ....................................................................................................... 11 2.4.4 Kivcet flash furnace ............................................................................................................................. 15 2.4.5 Contop furnace .................................................................................................................................... 15 2.4.6 QSL Process......................................................................................................................................... 16 2.4.7 Mitsubishi Process ............................................................................................................................... 16 2.4.1 Reverbatory Furnace ........................................................................................................................... 17 2.4.1 ASARCO Anode Furnace ..................................................................................................................... 17 2.4.2 Crucible Furnace ................................................................................................................................. 18 2.4.3 Blast Furnace....................................................................................................................................... 18 2.5 CONVERTING OF COPPER MATTE ....................................................................................................... 19 2.5.1 Peirce-Smith Converter ....................................................................................................................... 19 2.5.1 Hoboken Converter .............................................................................................................................. 20 2.5.1 Inco Oxygen Top Blown Nitrogen Stirred Converter .......................................................................... 20 2.5.2 Solid Matte Outokumpu Flash Converter ............................................................................................ 21 2.6 FIRE REFINING AND CASTING OF COPPER ANODES ....................................................................... 22 2.7 CAPTURE OF SULFUR GAS FROM SEMELTING AND CONVERTING ............................................. 23
3.
SECONDARY COPPER PRODUCTION ...................................................................................................... 24 3.1 INTRODUCTION ............................................................................................................................................. 24 3.2 UTILIZATION CYCLE OF COPPER CONTAINING MATERIALS ....................................................... 24 3.3 CATEGORIES OF COPPER SCRAP .................................................................................................................... 25 3.3.1 Types of copper alloys present in new scrap (Mike Laney, 2006): ...................................................... 26 3.4 COPPER SCRAP SORTING, PROCESSING AND BENEFICIATION ......................................................................... 27 3.4.1 Copper wire processing ....................................................................................................................... 27 3.4.2 Copper recovery from automotive scrap ............................................................................................. 29 3.4.3 Copper recycling from Electronic Scrap (E-scrap) ............................................................................. 30 3.5 SECONDARY COPPER PROCESSING PLANTS .................................................................................................... 33 3.5.1 New technologies in secondary copper smelting ................................................................................. 35 3.6 ISAMELT SECONDARY COPPER PROCESSING PLANTS .................................................................................. 37 3.6.1 UMICORE in Hoboken (Belgium) ....................................................................................................... 37 3.6.2 AURUBIS (Httenwerke Kayser) in Lunen (Germany) ....................................................................... 38
4. 5.
REFERENCES .................................................................................................................................................. 39 GLOSSARY OF TERMS.................................................................................................................................. 40
III
List of Figures
Figure 1 : Global refined copper demand in thousands of metric tons (Eurocopper, 2010) ..........................................1 Figure 2 : Production of refined copper worldwide (thousands of metric tons) (Eurocopper, 2010) ............................2 Figure 3 : Pyrometallurgy of copper (Biswas, 2002) .....................................................................................................4 Figure 4 : Hydrometallurgy of copper (Biswas, 2002) ..................................................................................................5 Figure 5 : Floating circuit for copper sulfide (Biswas, 2002) ........................................................................................6 Figure 6 : Effects of collector concentration and pH on the floatability (Biswas, 2002) ...............................................6 Figure 7 : Control system for an Outokumpu flash furnace (Biswas, 2002) .................................................................8 Figure 8 : ValeInco flash furnace (Biswas, 2002) .........................................................................................................9 Figure 9 : Noranda furnace (Biswas, 2002) ................................................................................................................. 10 Figure 10 : El Teniente furnace (Biswas, 2002) .......................................................................................................... 10 Figure 11 : Schematic of a Ausmelt furnace (Ausmelt, 2010)..................................................................................... 12 Figure 12 : Market acceptance of TSL technology (Ausmelt, 2010) ........................................................................... 12 Figure 13 : Integrated smelting and converting (Ausmelt, 2010) ................................................................................ 13 Figure 14 : Mount ISA copper ISAMELT smelter (ISAMELT, 2010) ....................................................................... 14 Figure 15 : Kivcet Flash Smelter (MetSoc, 2010) ....................................................................................................... 15 Figure 16 : Mitsubishi Process (Biswas, 2002) ........................................................................................................... 16 Figure 17 : Reverbatory Furnace (Biswas, 2002) ........................................................................................................ 17 Figure 18 : ASARCO Anode Furnace (Biswas, 2002) ................................................................................................ 17 Figure 19 : Crucible tilting furnace (Majoreng, 2010)................................................................................................. 18 Figure 20 : Blast furnace (Majoreng, 2010)................................................................................................................. 18 Figure 21 : Peirce-Smith Converter (Biswas, 2002) .................................................................................................... 19 Figure 22 : The Hoboken cconverter (Biswas, 2002) .................................................................................................. 20 Figure 23 : Nickel-Copper extraction at Copper Cliff (TMS, 2010) ........................................................................... 20 Figure 24 : Oxygen Top Blown Nitrogen Stirred Converter (TMS, 2010).................................................................. 21 Figure 25 : Outokumpu Flash Converter at Kennecott Utah (TMS, 2010).................................................................. 21 Figure 26 : Anode furnace casting wheel (Biswas, 2002) ........................................................................................... 22 Figure 27 : Producing sulfuric acid from smelting and converting gases (Biswas, 2002) ........................................... 23 Figure 28 : Diagram showing the flow of copper-containing materials (Goonan, 2010) ............................................ 24 Figure 29 : Process flow chart for copper scrap (Goonan, 2010) ................................................................................ 27 Figure 30 : Electrical cable grinder-separator - mod. RC (cogelme, 2010) ................................................................. 28 Figure 31 : Eddy current separator (Dings, 2010) ....................................................................................................... 28 Figure 32 : Flow sheet for recovering metals from scrap automobiles (Biswas, 2002) ............................................... 29 Figure 33 : Printed circuit board (PCB) recycling equipment (hnsxjx, 2010) ............................................................. 31 Figure 34 : Low-grade copper recovery (Biswas, 2002) ............................................................................................. 32 Figure 35 : Spectramet Alloy Sorter System (WTE, 2010) ......................................................................................... 32 Figure 36 : High-grade brass and bronze alloying (Biswas, 2002) .............................................................................. 33 Figure 37 : Umicore recycling smelter (Umicore, 2010) ............................................................................................. 37 Figure 38 : Kayser Recycling System (Aurubis, 2010) ............................................................................................... 38
IV
List of Tables
Table 1: Estimated distribution of impurities in flash furnace smelting (Biswas, 2002) ...............................................7 Table 2: Energy consumption comparison (ISAMELT, 2010).................................................................................... 14 Table 3: Old copper scrap generation and disposition in Japan (Biswas, 2002) .......................................................... 25 Table 4: 2006 metal demands for electronics equipments (Christian Hageluken, 2008)............................................. 30 Table 5: Typical Types of Copper Scrap Processed to Produce Secondary Copper .................................................... 34 Table 6: Major U.S. Scrap Copper User Categories (Mike Laney, 2006) ................................................................... 35 Table 7: IPPC-BAT for Secondary Copper Smelters (IPPC, 2010) ............................................................................ 36 Table 8: Recent copper smelters .................................................................................................................................. 36
TERM PAPER
ENGR 5187 Solid Waste Processing and Recycling Copper Recycling
Date: March 24, 2010 REV 1.0 PAGE: 1
1.
INTRODUCTION
Mankind has been using copper for more than 10,000 years. 6,000 years ago the discovery of Bronze (copper-tin alloy) revolutionized the manufacturing of metal artifacts. The Bronze age is characterized by advanced metalworking, and intensive copper recycling with the metal from damaged weapons and tools being reused. The village of Titelberg, Luxembourg (Wikipedia, Titelberg, 2010) had one of the first bronze recycling smelters of Europe (SHAW, 2007). Nowadays copper continue to have a leading role in various industrial applications. For instance, it recently replaced aluminum in Integrated Circuits (Wikipedia, 2010), and in Europe was chosen as the best metal for the new Euro currency; in the first phase of coins implementation (2002), 180.000 tons of copper were used in the coinage process (Eurocopper, 2010).
1.1
THE COPPER INDUSTRY This red metal is an essential resource in both the developed and developing economies, with a global demand for refined copper growing continuously, from 500 thousand tons in 1900 to more than 18 million tons in 2007, with an average annual growth rate of 4% since the 1990s (Fig. 1).
Figure 1 : Global refined copper demand in thousands of metric tons (Eurocopper, 2010) In 2007 the worldwide copper usage, including the direct reuse of scrap, was 22.8 million tons. Coppers main physical and mechanical properties (best electrical and thermal conductor, malleable, durable and antimicrobial) make it irreplaceable in the current human civilization. Copper is used in renewable energy production, improving energy efficiency, in sustainable construction, in transport and hospital equipment, and in various new technologies. The world mine capacity has risen, from 9.6 million in 1980 to 17.9 million tons in 2007, but copper recycling continue to have a very important role in the production of this metal.
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1.2
COPPER PRODUCTION AND USAGE The total production of refined copper is obtained with the sum of primary production (metal from extraction) and secondary production (recycling of copper scrap). The primary copper production worldwide reached 15.3 million tons in 2007. With an additional 2.8 million tons of secondary copper production, the total refined production is 18.1 million metric tons. Asias represents enormous copper production (figure 2), and in 2006, China alone accounted for 17.5% of global production. The refining capacity (2.3 million tons) is exceeding the mine output in 0.7 million tons. Most European copper producing countries, with the exceptions of Russia and Poland, import copper in the form of concentrates from countries such as Chile, Mexico and Indonesia.
Figure 2 : Production of refined copper worldwide (thousands of metric tons) (Eurocopper, 2010) The current overcapacity of copper smelting is causing some problems in the copper industry, some companies are on red ink (Aurubis, 2010) and others are acting to avoid financial problems.
TERM PAPER
In a recent announcement, Xstrata Canada (Xstrata, 2010) revealed that they plan to close the Kidd Metallurgical operations in May of 2010; Claude Ferron, Chief Operating Officer for Xstrata Copper Canada, commented about the Timmins smelter shutdown as follows: Global smelting overcapacity is driving treatment and refining charges to record lows while the costs to operate and maintain these facilities continue to increase. Our situation in Canada is exacerbated by a strengthening Canadian dollar. The requirement for further capital investment in these plants and lower sale prices for some by-products including sulphuric acid have also negatively impacted the viability of these operations. We have investigated options to improve the situation and after careful consideration have made this difficult decision to permanently shut down the Kidd zinc and copper plant. Global copper usage currently stands at 22.8 million tons (Eurocopper, 2010), of which 63% is refined primary copper, 11% refined secondary copper (scrap and end of life products requiring a refining stage) and 26% directly re-melted scrap (scrap from throughout the copper value chain); this gives an overall recycling rate of 37%. The main copper using countries and regions are the European Union (EU) with 5.1 million tons, China (4.8), USA (3.1), Japan (1.9) and South Korea (1.3). In 2002, China became the largest national market for refined copper (up from 10% in 1996, to 21% of global demand in 2006). In 2009, refined copper use per inhabitant remains much higher in the more developed economies, such as the former EU15, the USA and Japan, where usage is around 9 kg/capita per year, compared with many of the developing countries, where the usage is 1-2 kg/capita per year. In Europe, the use of refined copper has the following distribution: 58% in the electricity and energy sectors (cables, generators, motors, transformers, etc) 26% in the construction area (faades, cladding, pipes, window and canopy uprights, roofs) 10% in Mechanical engineering (machine tools, coins, etc) 5% in the transportation industry 1% in other activities. Copper can be alloyed with other elements (zinc, tin, lead, nickel and aluminum) to be used in a wide range of industrial applications. It has high resistance to corrosion (the roof of the Hildersheim Cathedral remains intact from 1280), possesses antimicrobial properties (pure or in alloy forms), and is a 100% recyclable material.
TERM PAPER
2.
METALLURGY OF COPPER
This chapter describes the processing of copper from various ores and scrap.
2.1
INTRODUCTION The presence of copper in Earth crust is made in copper-iron-sulfide and copper sulfide. Minerals like chalcopyrite (CuFeS2), bornite (CusFeS4) and chalcocite (Cu2S) are the most common ones, and the copper concentration in these minerals in an ore body is low, with a typical 0.5% Cu in open pit mines, and 1 to 2% Cu in underground mines. Copper with 99.99% purity is produced from these ores using pyrometallurgy and refining (Fig. 3).
Figure 3 : Pyrometallurgy of copper (Biswas, 2002) Copper present in oxidized minerals (Malachite, Azurite, Cuprite, Chrysocolla) and Covellite (CuS) is usually extracted using hydrometallurgy (Fig. 4).
TERM PAPER
Figure 4 : Hydrometallurgy of copper (Biswas, 2002) 2.2 COPPER COMMINUTION Copper comminution is done typically in three stages: blasting, crushing and wet grinding. The blasting can be minimized in block caving mine operations, but the presence of rock-breakers and grinders in the comminution phase is constant. Grinding is usually done with one semi-autogenous or autogenous mill, and one or two ball mills, using a solid-liquid mixture (80% solids).
2.3
COPPER FROTH FLOTATION Grinded particles must be fine enough to allow an efficient flotation, and that size control is normally done using hydrocyclones (BISWAS, 2002) feeding the flotation units with the overflow outputs (Fig. 5).
TERM PAPER
Figure 5 : Floating circuit for copper sulfide (Biswas, 2002) In the flotation units, sulfide minerals are hydrophilic. With a hydrophobic treatment for copper, the mechanism to separate it from gangue minerals is created. A standard copper ore froth flotation cell is designed with heteropolar molecules as pulp reagents, making the selected mineral water repellent for a determined pH and concentration in the pulp (Fig. 6). Air bubbles streams are normally added to the floatation cells to facilitate the flotation process.
Figure 6 : Effects of collector concentration and pH on the floatability (Biswas, 2002)
TERM PAPER
2.4
FURNACES USED IN COPPER PRODUCTION The concentrate from the flotation cells consist mostly of sulfide minerals with some residues of gangue oxides (Al, Ca, Mg, Si, etc). Oxidizing these sulfides gives a sulfide-rich melt (matte) and an oxide-rich melt (slag). In the following equation we can see the existence of a balance in the oxygen to be given in the smelt process, having the main objective of generating a higher grade matte (CuFeS) without over oxidizing the copper: CuFeS2 + O2 CuFeS + FeO +SO2 That trade-off can be solved adding some silica to the smelting process, with the negative impact of additional energy needed to melt the silica and the increased complexity in the control of the reaction (matte settling time). The offgas from the smelting process contains SO2 that can be captured in gas scrubbers to produce sulfuric acid (acid plant), and the dust particles can be captured in bag-houses or electrostatic precipitators. The estimated distribution of impurities during flash furnace production of a 55% Cu matte is presented in table 1.
Table 1: Estimated distribution of impurities in flash furnace smelting (Biswas, 2002) Metal Copper Alkali, Al, Ti Ag, Au, Pt group Antimony Arsenic Bismuth Cobalt Lead Nickel Selenium Zinc Matte 99 0 99 30 10 15 40 20 50 75 15 Slag 1 100 1 30 10 5 55 10 45 5 45 Volatilized 0 0 0 40 80 80 5 70 5 20 40
TERM PAPER
2.4.1
Outokumpu flash furnace Outokumpu flash furnaces (Fig. 7) may vary in size and shape, but normally they have the following particular characteristics: Concentrate burners (1 to 4) to add dry particulate feeds with O2 bearing blast and blow them downward into the furnace. Reaction shaft for O2 and Cu-Fe-S feed particles. Molten matte and slag droplets settler to form separate layers. Removal of the molten matte and slag thru water-cooled copper block tap holes. One uptake for removing hot SO2-bearing offgas. Outokumpu flash smelters are responsible for more than half of Worlds Cu matte smelting. Outokumpu smelters are also used for direct-to-copper smelting and for continuous converting. The wide adoption of Outokumpu flash smelting is due to its efficient capture of SO2, rapid production rate and its small energy requirement. Outokumpu smelters have an important handicap: the inability to smelt scrap.
Figure 7 : Control system for an Outokumpu flash furnace (Biswas, 2002)
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2.4.1
ValeInco flash furnace The Inco flash furnace (Fig. 8) uses industrial oxygen blast to smelt Cu-Fe-S and Ni-Cu-Co-Fe-S concentrates, producing high Cu and high Ni-Cu-Co mattes. It uses an input of concentrate dry feed and industrial oxygen through four horizontal burners. The SO2 offgas is removed through a central gas exhaust, and after a water-quenched treatment, is processed in the sulfuric acid plant. Very little nitrogen enters the Inco furnace so its blast and offgas handling Systems are small. Also, the offgas is strong in SO2, 60-75 volume%, ideal for SO2 capture. The slag phase can contain less than 1% Cu so it can be discarded without Cu-recovery treatment. This gives it a cost advantage over most other modem smelting techniques. Also, converter slag can be recycled through the furnace for Cu recovery, but this procedure will cause disturbances in a very stable smelting process.
Figure 8 : ValeInco flash furnace (Biswas, 2002) ValeInco flash smelting process has some disadvantages when compared with the Outokumpu flash smelting: more burners less efficient thermal design lack of offgas heat removal.
TERM PAPER
2.4.2
Noranda and El-Teniente bath smelting furnace The Noranda and El-Teniente smelting furnaces use a large (5 m x 20 m long) cylindrical shape barrel (Fig. 9 and 10), and they always contain layers of molten matte (72-75% Cu) and slag. The concentrate oxidation is done blowing oxygenenriched air through tuyeres into the furnace's molten matte layer.
Figure 9 : Noranda furnace (Biswas, 2002) The Cu-Fe-S input is dried and blown into the furnace using 3 to 10 submerged dedicated tuyeres. Moist (8% Water), flux, scrap and recycle materials and scrap are inserted using an end wall. The furnace output products are: high-grade molten matte (72 to 75% Cu) slag (typically with 6% of copper) SO2 offgas.
Figure 10 : El Teniente furnace (Biswas, 2002)
TERM PAPER
These furnaces can rotate to remove the liquids from the tuyeres, to unclog them when the blowing is defective. The submerged blast blowing method causes violent stirring of the matte-slag bath, resulting in a very fast melting and oxidation of the furnace content, and preventing the excessive deposition of solid magnetite in the furnace walls during highly oxidizing conditions. This violent stirring also permits extensive smelting of scrap and reverts. Noranda and Teniente furnaces are vastly used in Chile and account for 15 to 20% of world copper smelting.
2.4.3
AUSMELT and ISAMELT furnace The biggest disadvantage of flash smelting is the use of fine particles that generate problematic quantities of dust, requiring large settling areas to be built into the furnace. To address this problem, in 1971, researchers at the CSIRO (Commonwealth Scientific and Industrial Research Organization) in Australia began investigating the use of top-lancing technology for injecting coal into tin slags with the objective of improving the reduction kinetics. This research led to the development of a technology suitable for a variety of pyrometallurgical applications, including the smelting and converting of sulfide concentrates. This technology is now sold by two dominant organizations in smelting technology: AUSMELT (AUSMELT, 2010) and ISAMELT from Xstrata (ISAMELT, 2010). When compared with other smelting systems, the use of this type of smelting furnaces will result in a low cost, smaller and less complex gas handling system. The acid and sulphur fixation plants for these furnaces are more efficient, with optimized fuel and air-oxygen delivery systems, materials handling and feeding systems. The input feeding uses standard equipments with no need for drying or grinding of furnace input materials.
2.4.3.1
AUSMELT furnace This technology uses a proprietary top submerged lance (ATSL), and is based on reactions between the sulphidic and metallic components of the feed material and contained oxygen and ferric oxide in the bath. Critical process phenomena including feed material dissolution, energy transfer, reaction and primary combustion all take place in the slag layer. The intense agitation in the vessel ensures that reactions occur rapidly and residence times are low, because of the use of a vertically suspended lance, submerged in the molten slag bath. Process gases (air & oxygen) and fuel are injected through this lance, and the fuel is combusted at the lance tip to provide heat to the furnace. The slag is mixed by the pressure generated with injection of the process gases, and a controlled swirling of the process air in the lance, cools the exterior of the lance and allows the solidification of a slag layer on it. This solid slag layer protects the lance (Fig. 11) against the highly aggressive environment inside the furnace.
TERM PAPER
The AUSMELT lance is similar to tuyeres, and is designed to deliver precise quantities of process gas to the reaction medium (the slag), with the advantage of not suffering blockages or tuyere line refractory wear out. The degree of process oxidation and reduction is controlled by adjusting the fuel to oxygen ratio supply to the lance, and the proportion of reducing coal feed. This enables the furnace to be operated through a range of extreme oxidising to extremes reducing states.
Figure 11 : Schematic of a Ausmelt furnace (Ausmelt, 2010) AUSMELT currently have the status Technology of Choice, with more than 34 commissioned furnaces, 14 in copper production. The comparatively low capital and operating costs, and excellent environmental performance, is causing the abandonment of other smelting technologies in new projects.
Figure 12 : Market acceptance of TSL technology (Ausmelt, 2010)
TERM PAPER
AUSMELT furnaces can be integrated in a smelting and converting circuit (Fig. 13), producing blister copper from primary and secondary copper materials.
Figure 13 : Integrated smelting and converting (Ausmelt, 2010) The choice of furnace depends on the least expensive energy available (natural gas, fuel oil, electricity, etc). Choosing electric furnaces for the metal settling will allow a better control of the operating oxygen potential. An electric settling furnace allows the launder to be connected to the furnaces, with the relative heights of the furnaces adjusted, allowing the molten converter slag to flow from the converter to the settler. In this layout granulated or crushed matte is fed directly to the converter. The key advantage of this circuit is the reuse of the contained heat in the recycled converter slag, lowering the overall energy consumption of this integrated solution. AUSMELT Technology also processes a range of high and low-grade copper bearing secondary materials to produce black copper, converter grade copper or copper alloys. The range of secondary materials includes metallic scrap, alloys, reverts, residues, dusts and other recyclable copper-bearing materials such as electronic and computer scrap (Matusewic R W, 2010). The Ausmelt furnace system can handle coarse and fine-sized secondary materials. Solids fed to the furnace are shredded or crushed, while fine feeds can be agglomerated to prevent entrainment by offgases before reaching the slag bath. Organic and/or halide compounds present in some scrap are broken down during processing to benign compounds in the slag bath.
TERM PAPER
2.4.3.2
Xstrata ISAMELT smelting technology Using the same patented lance technology (J.Floyd, 1993) present in AUSMELT, the ISAMELT process provides a separated path solving some of the operational problems of this type of furnaces (Fig. 14). The three major breakthroughs from ISAMELT are: Low pressure drop operation. Accretion minimization with a redesigned sealed offgas circuit. The major refractory wear out mechanism was identified and minimized. Table 2: Energy consumption comparison (ISAMELT, 2010) Comparison of copper ISAMELT energy consumption with the original roasterreverbatory furnaces Roaster-reverb Copper ISAMELT furnaces plant Concentrate treated (ktpa) 650 1,070 Coal used (tpa) 85,000 6,300 0 6,120 Natural gas used (kN Oil used (kL/year) 2,400 1,980 Energy consumption per tonne of 4.12 0.47 concentrate (GJ/t)
The energy savings using ISAMELT/AUSMELT are well known (Table 2), and more than 50% of new projects plan to use this technology.
Figure 14 : Mount ISA copper ISAMELT smelter (ISAMELT, 2010)
TERM PAPER
2.4.4
Kivcet flash furnace The Kivcet Furnace (Fig.15) was developed in the USSR for smelting complex copper concentrates containing lead, zinc and other impurities. Dried concentrate is introduced tangentially into a small water-cooled cyclone where it is autogenously flash smelted with technical oxygen. The products pass into a partition chamber where they melt and off-gases are separated. The liquid metal flows into a settling kernel by passing below a vertical water cooled partition wall, immersed in the melt. The partition wall prevents reactor gases from entering the settling kernel from the partition chamber. The settling kernel is direct resistance heated. Settling of matte and slag takes place under a reducing atmosphere which is maintained by adding coke fines. The Kivcet process has the potential to be developed into a continuous or single step smelting process for treating complex concentrates.
Figure 15 : Kivcet Flash Smelter (MetSoc, 2010) This furnace has various benefits associated with it, and when compared to the old sintering and blast furnaces, the Kivcet smelter can reduce particulates (smoke) in the environment by 90% and the metals emissions by 70% to 90%. 2.4.5 Contop furnace The German company KHD Humboldt Wedag AG developed this furnace type in 1979. Using this furnace, this process combines autogenous oxygen flash smelting in a water-cooled cyclone with top blowing of the resulting high-grade matte (up to 80% Cu) and slag in separate, interconnected chambers. CONTOP means Continuous smelting and TOP blowing.
TERM PAPER
2.4.6
QSL Process In Queneau-Schumann-Lurgi (QSL) smelting process, the copper concentrate, the recycled flue, and a fluxing agent are wet, mixed and compacted to pellets before being fed to this furnace. Like the Kivcet furnace, the oxidation and blast furnace (reduction) are combined into one autogenous direct reduction unit.
2.4.7
Mitsubishi Process This continuous system merges the smelting and converting furnaces with an intermediate electric slag cleaning furnace (Fig. 16). It produces two continuous, high SO2 strength offgas streams for high volume sulphuric acid production. The main advantages over other copper furnaces is the simplicity of the copper recovery from slag, the flexibility in treating a wide range and grade of concentrates and secondary materials such as refinery anode scrap and copper scrap. It has the disadvantage (compared to single-furnace) of having has two offgas streams rather than one. With system improvements, the productivity of the Mitsubishi process was increased with: Increased oxygen-enrichment of smelting and converting furnace 'blasts'. Increased core life due to better refractory insulation, increased water cooling and improved lance tip positioning. Improved process control with the use of a real time temperature measurement system, and an expert system assisting the plant control.
Figure 16 : Mitsubishi Process (Biswas, 2002)
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2.4.1
Reverbatory Furnace All reverbatory (roof radiating) furnaces were decommissioned in the USA, because of a high cost of operation and environmental issues. Old units can be upgraded with oxy-fuel burners (Fig. 17) and be used to recycle low-grade copper scrap.
Figure 17 : Reverbatory Furnace (Biswas, 2002) 2.4.1 ASARCO Anode Furnace ASARCO anode furnaces are fed with blister copper with purity of more than 98%, but containing too much sulphur and oxygen. This anode furnace uses a tuyere to blow natural gas into the copper melt to burn off the oxygen. Initially in this process, a tall yellow flame billows from the top of the anode furnace, and when the oxygen present in the copper is gone, the flame becomes blue-green (Fig. 18).
Figure 18 : ASARCO Anode Furnace (Biswas, 2002)
TERM PAPER
2.4.2
Crucible Furnace Crucible furnaces are used for large amount of secondary copper production, using hydrocarbon gases and oils as the combustible. Normally used in foundries to melt clean (and well segregated) scrap. This furnaces can be stationary or tilting (Fig. 19).
Figure 19 : Crucible tilting furnace (Majoreng, 2010) 2.4.3 Blast Furnace Blast furnaces are used with low-grade copper and brass scrap, refinery slags, drosses, and skimmings. If this furnace is used exclusively to melt scrap, and has no chemical reduction involved, it is called a cupola furnace. The product of the blast furnace is normally called black copper.
Figure 20 : Blast furnace (Majoreng, 2010)
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2.5
CONVERTING OF COPPER MATTE The objective of the converting phase in the metallurgy of copper is the oxidation of molten Cu-Fe-S matte, and the creation of the more pure 'blister' copper (99% Cu). A large number of copper smelters use old and inefficient copper smelting technology, and in the smelting of primary copper, a low to medium grade matte is produced. In a converting phase, oxidation must remove between 30 to 80% of the sulphur present in the mined concentrate. Old converter technologies like the Pierce-Smith, the Hoboken and the inspiration converter, use the traditional two-cycle batch process with some operational problems: Intermittent gas flows of variable SO2 strength and gas flow rate. Ingress of air around the off-gas collection hood which dilutes the gas. Slow ladle transfers and repetitive handling of matte and slag, always with a handling danger and sulphur (gas) fugitive emissions. The thermal cycling and the bath composition will reduce the refractory life Because of these problems, alternative continuous converting processes have been studied with some field implementations: Downward lance Mitsubishi converting. Solid matte Outokumpu flash converting. Submerged tuyere Noranda continuous converting.
2.5.1
Peirce-Smith Converter The mature side-blown Peirce-Smith converter (Fig. 21) is widely used in the metallurgic industry, and after more than 80 years the Peirce-Smith type continues to dominate the copper industry that still use converters. Through many decades of usage, many mechanical and metallurgical improvements have been introduced, but the original concept remains the same.
Figure 21 : Peirce-Smith Converter (Biswas, 2002)
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2.5.1
Hoboken Converter The Hoboken converter (Fig. 22) is designed with an inverted u-shaped side flue at one end to siphon gases from the interior of the converter directly to an offgas collection system. The siphon results in a slight vacuum at the converter mouth.
Figure 22 : The Hoboken cconverter (Biswas, 2002) 2.5.1 Inco Oxygen Top Blown Nitrogen Stirred Converter This converter is used in the Copper Cliff plant (Fig. 23), and uses a combination of top blowing and bottom stirring with a simplified feeding technique. The application of nitrogen through porous plugs to facilitate stirring has been introduced. Input feeding is accomplished by gravity introduction of dry, nonagglomerated concentrate (90% -44 m) through a water-cooled pipe (Fig. 24) onto the "eye" created by the nitrogen. Supplemental heat is provided in the area to promote melting. Feeding zones and converting zones are separated so that gas velocity around the feed stream is minimal, minimizing the dusting rate to 1.5-2%.
Figure 23 : Nickel-Copper extraction at Copper Cliff (TMS, 2010)
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The gentle bottom stirring with nitrogen promotes desulfurization of the molten blister and enhances the approach to chemical equilibrium.
Figure 24 : Oxygen Top Blown Nitrogen Stirred Converter (TMS, 2010)
2.5.2
Solid Matte Outokumpu Flash Converter This converter (Fig. 25) is an efficient matte oxidation system, with an excellent recollection of the offgas and dust. The extra energy needed to process the matte feed, and the inefficient operation melting scrap copper are the principal disadvantages.
Figure 25 : Outokumpu Flash Converter at Kennecott Utah (TMS, 2010)
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2.6
FIRE REFINING AND CASTING OF COPPER ANODES The final step of the pyrometallurgical copper production is electrorefining. In the electrorefining process, thin and strong smooth anodes are needed for interleaving with cathodes in the electrorefining cells. The formation of surface blisters is prevented by removing sulphur and oxygen from the converter molten copper by air oxidation and hydrocarbon reduction. The air (S removal) and hydrocarbons (O removal) are usually injected into the molten copper via one or two submerged tuyeres in a rotary 'anode' furnace (Fig. 18). Anodes are usually cast in open molds on a large rotating wheel (Fig. 26). Uniformity of anode mass is critical for efficient electrorefining so most smelters automatically weigh the amount of copper poured into each anode mold.
Figure 26 : Anode furnace casting wheel (Biswas, 2002)
The cast anodes are often straightened and flattened in automated anode preparation machines. Their lugs are normally machined to a knife-edge. Straight, flat, vertically hung anodes are required to give pure cathodes and high current efficiencies in the electrorefinery process. Smelters and refineries can reject 2 or 3% of their new anodes because of physical defects or incorrect masses. They also produce 15 to 20% un-dissolved anode scrap after a completed electrorefining cycle. These two primary scrap materials return to the rotary 'anode' furnace to be re-melted and cast into new anodes, going in a new feed to another electrorefinery cycle.
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2.7
CAPTURE OF SULFUR GAS FROM SEMELTING AND CONVERTING The smelting and converting of sulphide copper ore (85% of the world copper ores offering) involves the extraction of the sulphur present in the concentrates. In that extraction process a dangerous and environmental destructive gas (SO2) is produced, requiring a SO2 gas processing unit; the smelter acid plant (Fig. 27).
Figure 27 : Producing sulfuric acid from smelting and converting gases (Biswas, 2002) The current smelting techniques used to process sulphide copper concentrates are typically producing 2.5 to 4.0 tonnes of sulphuric acid per tonne of produced copper. High sell prices and stable production of the sulphuric acid byproduct, will help the profitability and a fast return of the investment (ROI) in copper production plants.
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3.
SECONDARY COPPER PRODUCTION

The previous sections gave a description of some of the equipments and processes used in the primary and secondary copper production. This chapter will give a detailed description of the secondary copper production, with emphasis in the latest technologies used in the copper recycling industry.
3.1
INTRODUCTION The production of copper from scrap can be justified with following reasons: Price, it is cheaper to recycle copper than to extract new copper. Limited resources, 12-13% of all known reserves have been mined. Energy efficiency, recycling a ton of copper saves 85% of the energy that would be used to mine and extract the same ton of copper. Landfill costs, waste from household and industry is usually dumped in holes in the ground (landfill), that are rapidly getting filled up and becoming a very expensive away to dispose waste. Environment, less gases and dust are released in the recycling of copper.
3.2
UTILIZATION CYCLE OF COPPER CONTAINING MATERIALS Copper is one of the metals that is present in all types of electrical equipment, and it has a strong presence in non-electrical equipment. The U.S. geological survey circular 1196-x, summarizes the flow (figure 28) of copper containing materials in our actual human civilization.
Figure 28 : Diagram showing the flow of copper-containing materials (Goonan, 2010)
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Figure 28 shows that the semi and finished product fabricators generate an impressive 735,000 metric tons of new scrap copper, when compared with the 1,920,000 of old scrap. This reinforces the idea that the recycling of old scrap needs to be more efficient, to lower the segregation and processing costs. Some of the viability problems that exists in the processing of old scrap are well known: Segregation problems, old copper scrap mixed with other materials. Unpredictability, irregular day to day flow of scrap to be recycled, causing storage or underproduction operational costs. Logistics, old copper scrap is scattered through multiple locations. As a result, old scrap will stay in warehouses, junkyards and landfills (table 3), if the price is not competitive to recycle the copper. Table 3: Old copper scrap generation and disposition in Japan (Biswas, 2002) Source of Scrap Power cables, Analog cables Electric Appliances, Machinery Automotive Industrial machines, ships, cars Buildings Totals Disposed 197 142 79 62 118 598 Collected 197 29 38 51 81 396 Landfilled 0 113 41 11 37 202 %Recycled 100 20 48 82 69 66
3.3
CATEGORIES OF COPPER SCRAP The most common categories of copper scrap are: Number 1 scrap, with a minimum copper content of 99% and a minimum thickness of 1.6 mm. Number 2 scrap, with a minimum copper content of 96%, in the form of wire, heavy scrap, or nodules Light copper, with a minimum copper content of 92% (gutters, downspouts, boilers, kettles), generally containing minimal levels of alloyed copper. Refinery brass, scrap from various copper alloys with a minimal copper content of 61.3%. Copper-bearing scrap, all low-grade materials such as skimmings, sludges, slags, reverts, grindings and other residues. Copper wastes are a special category of scrap, and are characterized by a poor copper content and high processing costs (PCB etchants, copper mixed with radioactive materials, etc).
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3.3.1
Types of copper alloys present in new scrap (Mike Laney, 2006): Copper is intensively used in the electrical industries in pure form (>99%) because of the excellent electrical and thermal conductivity, but to obtain extra mechanical properties is alloyed with a myriad of metals, the most common alloys of copper are: Beryllium-copper, with the addition of beryllium (0.52.0 percent by weight) this copper alloy will exhibit high electrical and thermal conductivity, good corrosion and fatigue resistance, high strength and hardness, and nonmagnetic properties. Cadmium-copper, with the addition of cadmium (0.81.2 percent by weight) this copper alloy will exhibit a double mechanical strength and wear resistance of pure copper, will retaining 90 percent of its conductivity; this alloy is widely used in contact wire and catenary strand. Chromium-copper, with the addition of chromium (0.61.2 percent chromium by weight) this copper alloy will exhibit twice the mechanical strength of pure copper, while retaining 85 percent of its conductivity, and obtaining an excellent corrosion protection. Aluminum-copper and copper-aluminum, the copper content of copperaluminum alloys ranges from about 70 to 90 percent copper (average copper content is about 85 percent by weight), the balance being aluminum and perhaps small amounts of other elements. Bolts, bushings, cams, and gears made from these materials are corrosion resistant with good strength. Aluminum bronze is a type of bronze in which aluminum is the main alloying element added to copper. Aluminum bronzes are most valued for their higher strength and corrosion resistance compared with other bronze alloys. They have low oxidation rates at high temperatures and low reactivity to sulfurous compounds and other exhaust products of combustion. They are also resistant to sea water corrosion. Aluminum bronze castings have exceptional corrosion resistance; high strength, toughness, and wear resistance; and good casting and welding characteristics. Nickel-copper and copper-nickel alloys include cupronickels (6888 percent copper and 1030 percent nickel) and nickel silvers (5565 percent copper, 1225 percent nickel, and 327 percent zinc). Because copper-nickel alloys are corrosion and oxidation resistant and thermally stable, they are used in marine and powerplant applications, such as condenser tubes, valves, pumps and fittings. Bronze, the copper-tin alloys or tin bronzes (7090 percent copper, 512 percent tin, balance other metal) have good corrosion resistance and are stronger and more ductile than brass. Additions of lead (612 percent) diminish alloy strength but enhance machineability. Brass, a copper-zinc alloy with 10 to 40% of zinc and other elements (lead, tin, etc); Brass is used in decorative and artistic applications, hardware, munitions, and plumbing.
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3.4
COPPER SCRAP SORTING, PROCESSING AND BENEFICIATION After the collecting of copper scrap, some processing paths need to be taken to get a recoverable copper, pure or in an alloy form (Fig. 29).
Figure 29 : Process flow chart for copper scrap (Goonan, 2010) 3.4.1 Copper wire processing Copper scrap wire and cable can be classified in three types: Aerial cables, predominantly high-voltage power cable, mainly copper with little insulation, and easy to recycle. Surface indoor/outdoor cables, various insulations and sections. Due to the lower sections of the conductor, the cost of processing per kg of recovered copper is higher than thicker cables. The mixing with other hardware (steel brackets, tie raps, etc) will require additional processing steps; the automotive harnesses is one example. Underground and submarine cables, characterized with a strong and complex construction, and multiple layers of metal and insulation. The recycling process of these cables can be complex and create environmental hazards. Standard cables can be chopped and sorted using compact cable grinders (Fig. 30). Special cables will require special equipments and recycling processes.
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Figure 30 : Electrical cable grinder-separator - mod. RC (cogelme, 2010) In cables with aluminum and copper conductors, Eddy-current separators can be used after the shredding of the cable to segregate metal from plastic (Fig. 31).
Figure 31 : Eddy current separator (Dings, 2010)
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3.4.2
Copper recovery from automotive scrap With the massive implementation of electronic technology in the automotive industry, more copper (and other metals) are present for the electrical system. Other components (Fig. 32) made of copper (radiators, tubes, etc) may need distinct segregation procedures.
Figure 32 : Flow sheet for recovering metals from scrap automobiles (Biswas, 2002) Copper electrical cabling present in automobiles, is characterized with thicker insulations to ensure mechanical and thermal protection for the conductors. This insulation can be removed from the wire with very fine chopping, producing a fine-particle mixture of insulation and wire, which can be segregated using a fluidized bed, separating the insulation (overflow) from the wire (underflow). Another copper-insulator separation process is the automated cable stripping, where the cable is passed slowly through a machine that separates the insulation from single strands of copper wire.
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3.4.3
Copper recycling from Electronic Scrap (E-scrap) With the astonishing technological advances of microelectronics, electronic appliances are having a premature end of life. Nowadays the end of life can be 6 months for a cell phone, 2 years for a note book, 3 years for a desktop PC, 4 years for some TV appliances, etc. The VHS video recording system took 30 years to reach the end of life (Wikipedia, Wikipedia, 2010), and was replaced by the DVD system. The DVD system, needed only 10 years of operational usage to become obsolete, and is currently being replaced by the high definition blue ray disc system. This premature end of life of the DVD system, is also sending to the scrap yard, tons of displays (low resolution CRT, LCD, Plasmas, etc), making even worse the scenario of the recycling the giant inventory of E-scrap waiting to be recycled. With a large number of different materials (metals, plastics, polymers, etc) present in E-scrap, copper continues to be the most used (Table 4).
Table 4: 2006 metal demands for electronics equipments (Christian Hageluken, 2008)
3.4.3.1
European Community WEEE Directive The European Community created in 2002 a directive (2002/96/EC), trying to attenuate the environmental problem caused by the E-scrap. The Waste Electrical and Electronic Equipment Directive (WEEE Directive) put some rules on the handling of the waste created by electrical and electronic equipment.
TERM PAPER
In February of 2003, the WEEE directive and the RoHS Directive (Restriction of Hazardous Substances Directive) was added to the European legislation, defining very restrictive rules in the collection, recycling and recovery targets for all types of electrical goods. The WEEE directive imposes the responsibility for the disposal of waste electrical and electronic equipment on the manufacturers of such equipment. Those companies should establish an infrastructure for collecting WEEE, in such a way that "Users of electrical and electronic equipment from private households should have the possibility of returning WEEE at least free of charge". Also, the companies are compelled to use the collected waste in an ecologically-friendly manner, either by ecological disposal or by reuse/refurbishment of the collected WEEE. 3.4.3.2 Equipments used in E-scrap recycling Recycling E-scrap is a challenging task, because of the complexity of the scrap. Manual removal of the electronic content from the metallic (steel, aluminum) cases of VCRs, computers, LCDs, etc, is the first segregation operation. After the initial segregation, inspection and stockpiling is needed to bin out the waste to the proper recycling procedures. The printed circuits boards are normally shredded, and processed using automatic equipments (Fig. 33).
Figure 33 : Printed circuit board (PCB) recycling equipment (hnsxjx, 2010) The grinded particles present at the output of this equipment can be additionally segregated using x-rays automated technologies (Fig. 35).
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Figure 34 : Low-grade copper recovery (Biswas, 2002) Burning, sweating and drying (Fig. 36) steps may be applied to the segregated particles; these extra processing steps add environmental issues with the possible emissions of toxic gases (Fig. 34). These problems, in combination with the associated extra costs incurred to the recycling operation, make single step recycling processes the most wanted technology for new recycling plants.
Figure 35 : Spectramet Alloy Sorter System (WTE, 2010)
TERM PAPER
Figure 36 : High-grade brass and bronze alloying (Biswas, 2002)
3.5
SECONDARY COPPER PROCESSING PLANTS Copper scrap (Table 5) can be processed in primary or secondary smelters. Primary smelters normally smelt copper concentrates, but some smelting designs are adapted to smelt all grades of scrap. The designs from Isasmelt, Mitsubishi, Noranda, reverberatory and top blown rotary converter smelting furnaces are some of the existing examples. Some copper scrap is also recycled in the converters of primary smelting plants. Standard secondary smelters (Table 6) use blast furnaces, top blown rotary converters and electric furnaces for smelting low-Cu grade scrap. In these old plants, the normal smelting output product is black copper (80% Cu), subsequently converted into rough copper (96% Cu), and then fire refined and casted into anodes (98.5% Cu). Because these processes cannot completely remove other metals (Ni, Sn, etc) from the recycled copper, the final step of electrorefining is required. Electrorefining also recovers silver and gold and other group metals, with the subsequent slime processing.
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Table 5: Typical Types of Copper Scrap Processed to Produce Secondary Copper
The secondary copper refining is more dirty than primary copper refining because of impurities present in the copper scrap. Therefore, bigger facilities are needed to house larger electrolyte purification tanks and slimes treatment units. Copper scrap recycling will slow down the process of the depletion of the copper present in earth's crust, and reduce energy costs associated with copper mining and mineral processing.
TERM PAPER
Table 6: Major U.S. Scrap Copper User Categories (Mike Laney, 2006)
3.5.1
New technologies in secondary copper smelting The future of secondary copper smelting in the world is experiencing a big revolution with the Ausmelt and Isasmelt top lance technologies. The United States is shutting down all old technology secondary smelters because of environmental and economical reasons. European Community under the IPPC directive (Integrated Pollution Prevention and Control) defined a set of best available techniques (BAT) with the objective of emissions reductions and environmental improvements. In the IPPC directive (IPPC, 2010) a comprehensive review of copper smelting and converting technologies for producing primary and secondary copper is presented.
TERM PAPER
Table 7: IPPC-BAT for Secondary Copper Smelters (IPPC, 2010)
Top lance smelting (bath smelting) is present in the majority of new and projected secondary smelters (Table 8). Table 8: Recent copper smelters
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3.6 3.6.1
ISAMELT SECONDARY COPPER PROCESSING PLANTS UMICORE in Hoboken (Belgium) The fuel savings and emissions control of the top lance technologies, compensate for the downtime that this system has in the periodical replacement of the top lance (30 to 60 minutes in a 10 day period). A state of the art recycling plant is present in Hoboken (Belgium) using the ISAMELT furnace as the core component of the pyrometallurgical process (Fig. 37).
Figure 37 : Umicore recycling smelter (Umicore, 2010)
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3.6.2
AURUBIS (Httenwerke Kayser) in Lunen (Germany)
The same technology is labelled with the name Kaiser Recycling System (KRS) in the Httenwerke Kayser AG (Aurubis, 2010) plant in Lunen (Germany).
Figure 38 : Kayser Recycling System (Aurubis, 2010) The KRS recycling plant was implemented using ISASMELT furnaces, replacing three blast furnaces and one Peirce Smith converter used for smelting residues and scrap copper. The benefits of using this technology can be summarized as follows: Improved overall copper recovery with a less copper present in the slag phase. Less furnaces in operation Decrease in offgas volume Production capacity exceeds the original design by 40% Energy consumption is down by more than 50% CO2 emissions down by more than 64% Overall emissions are 10% of the old plant.
TERM PAPER
4.
REFERENCES
Aurubis. (2010). Aurubis. (Aurubis) Retrieved from Aurubis: http://www.aurubis.com/en/home/ Ausmelt. (2010). Ausmelt. Retrieved from Ausmelt: http://www.ausmelt.com.au/PDF/Capability%20Statements/Ausmelt%20Copper%20Capability%2020 05%20%28LR%29.pdf Biswas, W. D. (2002). Extractive Metallurgy of Copper (4th edition). Oxford: Pergamon. Christian Hageluken, C. M. (2008). Mining our Computers. Stuttgart: EGG. cogelme. (2010). cogelme. Retrieved from cogelme: http://www.cogelme.com/eng/cable-weeerecycling-wire-stripper.htm Dings. (2010). Dings. Retrieved from Dings: http://www.dingsmagnets.com/industrial-magnetindustries/recycling.html Eurocopper. (2010). Eurocopper. Retrieved from Eurocopper: www.eurocopper.org Goonan, T. G. (2010). Copper Recycling in the United Sates in 2004. Virginia: US Department of the interior. hnsxjx. (2010). hnsxjx. (hnsxjx) Retrieved from hnsxjx: http://english.hnsxjx.cn/393.shtml IPPC. (2010). EU. (EU) Retrieved from EU: http://ec.europa.eu/environment/air/pollutants/stationary/ippc/index.htm ISAMELT. (2010). ISAMELT. Retrieved from ISAMELT: http://www.isasmelt.com/ J.Floyd. (1993). freepatentsonline. Retrieved from freepatentsonline: http://www.freepatentsonline.com/5251879.pdf Majoreng. (2010). majoreng. Retrieved from majoreng: http://www.majoreng.com.au/metals.tilting_crucible.php Matusewic R W, B. B. (2010). Ausmelt Technology for Recycling of Computer Board and Other High Value Materials. Retrieved from Ausmelt: http://ausmelt.com.au/PDF/Papers/Ausmelt%20Technology%20%20Recycling%20of%20Computer%20Boards.pdf MetSoc. (2010). MetSoc. Retrieved from MetSoc: http://www.metsoc.org/virtualtour/processes/zinclead/kivcetlarge.asp Mike Laney, P. P. (2006). Current Status of Secondary Copper Production in the United States. NC: RTI International. SHAW, M. L. (2007). THE NORTH SMELTER AT TITELBERG: POST-IMPERIAL BRONZE RECYCLING IN BELGIC GAUL. Columbia: University of Missouri. TMS. (2010). TMS. Retrieved from TMS: http://www.tms.org/pubs/journals/JOM/9601/Queneau9601.html#ToC6 Umicore. (2010). Umicore. (Umicore) Retrieved from Umicore: http://www.umicore.com/en/ Wikipedia. (2010). Retrieved from http://en.wikipedia.org/wiki/Copper_interconnect Wikipedia. (2010). Retrieved from : http://en.wikipedia.org/wiki/VHS Wikipedia. (2010). Titelberg. Retrieved from Wikipedia: http://en.wikipedia.org/wiki/Titelberg Wikipedia. (2010). Wikipedia. (wikipedia) Retrieved from Wikipedia: http://en.wikipedia.org/wiki/VHS WTE. (2010). Spectramet. (WTE) Retrieved from WTE: http://www.wte.com/html/new_technologies.html Xstrata. (2010). Xstrata. Retrieved from Xstrata: http://www.xstrata.com/media/news/2009/12/08/0702CET/200912080702.en.pdf
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5.
GLOSSARY OF TERMS
CCR - Canadian Copper Refinery (Montral), is an Xstrata plant that refines anode copper from the Horne and Altonorte smelters. Matte - Is an intermediate, more concentrated (with respect to the desired metal) material than concentrate, from which it is made, and is usually transferred to another furnace for further concentration. Copper mattes contain between 50 and 70 percent copper, depending on the process parameters. Slag partially vitreous by-product of smelting. Tuyere Tube, nozzle or pipe used to blow air into the furnace. Black copper Impure (ex:80%) copper obtained in a blast-furnace. Blister copper The product of a converting furnace. It is an intermediate, more concentrated (with respect to the desired metal) material than matte, from which it is made, and is usually transferred to another furnace for further concentration. Blister copper contains about 98 percent copper, the exact percentage depending on the process parameters. Blister copper is sometimes cast into ingot forms and placed into worldwide trade. Most often it is fire-refined onsite. The name origin derives from the blistered surface caused by the SO2 escape. New scrap (prompt scrap) generated in manufacturing processes (residues). Old scrap collected copper present in the final products or applications. No1 copper purity greater than 99%. No2 copper product with 94 to 98% of purity. Light copper 88 to 94% copper. Irony scrap small electric motors, shredded automobile copper fractions. Anode The positive terminal in an electrolytic cell where electrons leave a device to enter the external circuit. A copper anode at 99 percent purity will dissolve. Cathode The negative terminal in an electrolytic cell where copper is plated during electrowinning or electrolytic refining. Copper so plated is referred to as cathode and is generally about 99.99 percent pure. Anode slimes A mixture of metals and some insoluble compounds that originate in and dissolve from the anode during electrolysis and precipitate from the electrolyte onto the cell floor. These are processed for the metal content. In copper electrolysis, gold, silver, selenium, tellurium, and other metals are recovered. OFC - Oxygen-free copper OFHC - Oxygen-free high thermal conductivity copper. Copper concentrate - A product of flotation milling. It composes sulfide minerals and entrained material and contains one-third each copper, iron, and sulfur. It can be processed pyrometallurgically in a smelter to produce matte or hydrometallurgically (pressure leaching) to produce pregnant leach solution, both products requiring further processing to obtain copper metal. Copper concentrate may participate in worldwide trade or be smelted domestically in its country of origin.
TERM PAPER
Electrolyte - An acidic solution containing copper ions. In electrorefining, the concentration of copper ions remains relatively constant, in balance with copper dissolution at the anode and copper precipitation at the cathode. In electrowinning, the copper concentration is more variable but in relative equilibrium with new copper ions introduced by rich (copper-loaded) electrolyte from the solvent extraction facility and with the copper precipitation at the cathode. PCB Printed Circuit Board (or PWB for Printed Wire Board). Electrorefining - An electrolytic refining process where less pure copper anodes are dissolved, and high-purity copper is plated at the cathode. Electrowinning - An electrolytic refining process where the anode is inert, and rich (copper-loaded) electrolyte continually replaces lean (copper-depleted) electrolyte as copper is plated at the cathode. Flash smelting - Smelting process for sulfur-containing ores (chalcopyrite, etc) developed by Outokumpu in Finland, used for the first time in 1949 at the Harjavalta plant for smelting copper ore. It can be adapted for nickel and lead smelting. The flash process uses the autogenic principle of using the energy contained in the sulfur and iron (exothermic oxidation) for melting the ore. Fire-refined copper - The product of a fire-refining furnace. It is an intermediate, more concentrated (with respect to the desired metal) material than blister, from which it is made. Because oxygen is added in the processing to upgrade the copper content by oxidizing the impurities in the furnace charge materials, the resulting copper must be deoxidized, usually by stirring it with natural gas, with the carbon in the natural gas reacting with the excess oxygen. Fire-refined copper contains about 99 percent copper, the exact percentage depending on the process parameters. Firerefined copper is sometimes cast into ingot forms and placed into worldwide trade. Often it is transferred to another same-company electrorefining facility for processing into 99.99 percent copper cathode. Fire-refining is also used to purify high-grade copper scrap consumed at brass mills in the production of tube and sheet products. Flotation - A method of mineral separation in which air and a variety of reagents are injected to create a froth in water. Some finely crushed minerals float and other minerals sink. The preferential flotation of sulfide minerals and sinking of the gangue materials is used to concentrate the copper for economic smelting. The resulting product is called concentrate. Flux - Slag-making materials, such as sand, lime, limestone, that are added to hightemperature metal and metal-oxide emulsions to fuse the oxides into a relatively low melting-point material that can be readily separated from the molten metal. Pregnant leach solution - The metal-loaded acidic solution collected in a lined pond following percolation of acid through leachable ore piles. It is the feedstock for solvent-extraction operations. Primary copper - Copper extracted from ores and recovered as copper metal or copper-bearing chemicals. Secondary copper - Copper recovered from scrap and waste. Scrap types include clippings, cuttings, grindings, turnings, flue dust, slag, filter cakes, and spent electrolyte solutions.
TERM PAPER
ISRI Institute of Scrap Recycling Industries, Inc WEEE - Waste Electrical and Electronic Equipment Directive ROHS - Restriction of Hazardous Substances Directive Pyrometallurgy - A process of separating desired metals from materials under conditions of high heat. Hydrometallurgy - A process of separating desired metals from aqueous solutions. Sweating - heating below the melting point of copper and copper alloys scrap types that contain low-melting lead alloys. Raffinate - The copper-depleted flow back to the heap leach after the copper-rich pregnant leach solution has been stripped of its copper load through solvent extraction.

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ENGR5187 Solid Waste Processing and Recycling

Alberto Rui Frutuoso Barroso March 24, 2010 Laurentian University

Figure 6 : Effects of collector concentration and pH on the floatability (Biswas, 2002)

Figure 7 : Control system for an Outokumpu flash furnace (Biswas, 2002)

Figure 10 : El Teniente furnace (Biswas, 2002)

Figure 12 : Market acceptance of TSL technology (Ausmelt, 2010)

Figure 14 : Mount ISA copper ISAMELT smelter (ISAMELT, 2010)

Figure 16 : Mitsubishi Process (Biswas, 2002)

Figure 18 : ASARCO Anode Furnace (Biswas, 2002)

Figure 20 : Blast furnace (Majoreng, 2010)

Figure 21 : Peirce-Smith Converter (Biswas, 2002)

Figure 23 : Nickel-Copper extraction at Copper Cliff (TMS, 2010)

Figure 24 : Oxygen Top Blown Nitrogen Stirred Converter (TMS, 2010)

Figure 25 : Outokumpu Flash Converter at Kennecott Utah (TMS, 2010)

Figure 26 : Anode furnace casting wheel (Biswas, 2002)

SECONDARY COPPER PRODUCTION

Figure 28 : Diagram showing the flow of copper-containing materials (Goonan, 2010)

Figure 31 : Eddy current separator (Dings, 2010)

Figure 35 : Spectramet Alloy Sorter System (WTE, 2010)

Figure 36 : High-grade brass and bronze alloying (Biswas, 2002)

Table 5: Typical Types of Copper Scrap Processed to Produce Secondary Copper

Table 7: IPPC-BAT for Secondary Copper Smelters (IPPC, 2010)

Figure 37 : Umicore recycling smelter (Umicore, 2010)

AURUBIS (Httenwerke Kayser) in Lunen (Germany)

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