Anda di halaman 1dari 12

Resources, Conservation and Recycling 36 (2002) 6172

www.elsevier.com/locate/resconrec

Comparison of salt-free aluminum dross treatment processes


8 nlu Necip U a,*, Michel G. Drouet b,1
a

Metallurgical and Materials Science Engineering Department, Faculty of Chemistry -Metallurgy, Istanbul Technical Uni6ersity, 80626 Maslak, Istanbul, Turkey b PyroGenesis Inc., 1744 William Street, Suite 200 Montreal, Quebec, Canada H3J 1R4 Received 30 August 2001; accepted 24 January 2002

Abstract Dross is an unavoidable by-product of the aluminum production. It forms at the surface of the molten metal as the latter reacts with the furnace atmosphere. Depending on the process, it contains, on average, about 50% free aluminum metal dispersed in an oxide layer. Since the aluminum production is highly energy-intensive, dross recycling is very attractive from both the energy and the economic standpoints. The conventional recycling process using salt rotary furnaces is thermally inefcient and environmentally non-acceptable because of the production of salt slags. Several salt-free dross treatment processes have been proposed in the last few years, their operation, energy consumption and metal yield will be described in detail and compared in the present paper. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Dross recycling; Aluminum; Salt-free dross processing; Alcan plasma torch process; Droscar process; Alurec process; Ecocent process; Drosrite process

1. Introduction Every primary aluminum producer, remelter or recycler of aluminum is faced with the fact that, in all processes involving molten aluminum in contact with air,
* Corresponding author. Present address: Department of Materials Science and Engineering, University of Virginia, 116 Engineers Way, Charlottesville, VA 22904-4745, USA. Tel.: + 1-434-982-5692. 8 nlu E -mail addresses: nu4n@virginia.edu (N. U ), mdrouet@pyrogenesis.com (M.G. Drouet). 1 Tel. + 1-514-937-0002; fax: + 1-514-937-5757. 0921-3449/02/$ - see front matter 2002 Elsevier Science B.V. All rights reserved. PII: S 0 9 2 1 - 3 4 4 9 ( 0 2 ) 0 0 0 1 0 - 1

62

8 nlu N. U , M.G. Drouet / Resources, Conser6ation and Recycling 36 (2002) 61 72

a dross is formed as the molten metal reacts with the furnace atmosphere (MFS Engineering Ltd Catalogs, 1997). It generally represents from 1 to 10% of the melt and depending on the process, may contain, on average, between 30 and 60% free aluminum metal dispersed in an oxide layer, although higher and lower contents may occur (Ruff, 1998; Gripenberg et al., 1997). Traditionally, the recovery of the aluminum metal has been performed using the rotary salt furnace (RSF) process. In the RSF process, an oil or gas red furnace is charged with the dross, and a salt ux (up to 50% of the dross weight) is added. The salt protects the metal from the reactive atmosphere and facilitates agglomeration and separation of the metal, thereby increasing metal recovery. Fig. 1 shows the RSF process (Lavoie and Dube, 1991). Using salt brings some disadvantages such as its cost, environmental and safety hazards (Lavoie and Dube, 1991). The non-metallic by-product is referred to as salt cake, a mixture of aluminum oxides and aluminum nitrides, metal and salts. More than 1 ton of salt cake is produced for every ton of dross treated. The salt cake is a growing environmental problem (Gripenberg et al., 1995). Other drawbacks are that salt vapors are emitted from the furnace and the fact that the salt requires energy for melting and is costly to purchase, transport (Gripenberg et al., 1995). With the objective of developing a salt-free process, in the last 10 years, numerous R&D activities have been conducted at different locations around the world. In this paper, we will review the processes proposed by Hydro-Quebec and Alcan both from Canada, AGA and Hoogoven in Holland, Focon Foundry in Austria and more recently by PyroGenesis, again from Canada.

Fig. 1. The rotary salt furnace process (Lavoie and Dube, 1991).

8 nlu N. U , M.G. Drouet / Resources, Conser6ation and Recycling 36 (2002) 61 72

63

Fig. 2. The ow sheet of the entire plasma dross treatment process (Lavoie and Dube, 1991).

2. Dross treatment processes operating without salt

2.1. The Alcan plasma torch dross treatment process


This process, initially tested in 1987 at the Hydro-Quebec Research Center, has been in operation at the Alcan Treatment Center in Jonquieres, Canada, for the last 9 years. Instead of using a gas or fuel burner, as in the RSF, a plasma torch is used to provide the required heat for heating the charge in the rotary furnace. The torch is mounted on the charging door of the rotary furnace which is designed to maintain close control of the atmosphere composition. The plasma torch consists of two water-cooled internal electrodes separated by a small gap through which the process gas, such as air or nitrogen, is continuously injected. The dross is charged, the door is closed and the application of high voltage initiates an electric arc between the torch electrodes. The arc heats the gas to a very high temperature, causing the gas to dissociate and partially ionize. The charge is heated to 700 800 C while the furnace is rotated. The aluminum in the dross is nely divided and wrapped in oxide lms. The presence of the oxide lms results from the oxidation of the metal in contact with the reactive fossil fuel furnace atmosphere where the dross was initially produced. During heating of the dross by the plasma torch, which operates with air or nitrogen as the process gas, further oxides and nitrides are formed as the plasma gases react with some of the free metal contained in the dross. The rotation of the furnace provides mechanical stirring that ruptures the oxide lm, freeing molten metal and improving metal recovery. The oxide portion of the dross, termed non-metallic product (NMP), is a grayish powder containing mostly alumina with variable quantities of aluminum nitride and magnesium oxide

64

8 nlu N. U , M.G. Drouet / Resources, Conser6ation and Recycling 36 (2002) 61 72

depending on the alloy composition (Lavoie and Dube, 1991). Fig. 2 shows the ow sheet of the entire plasma dross treatment process.

2.2. The Hydro -Quebec DROSCAR graphite arc process


Hydro-Quebec has developed and patented a different salt-free technology using a rotary furnace heated by a direct current electric arc between two graphite electrodes called DROSCAR. The process is illustrated in Fig. 3 which shows the ow sheet of the entire dross treatment process (Drouet et al., 1994, 1995). DROSCAR uses a DC electric arc, stretched and maintained between the two graphite electrodes, to heat the charge above the aluminum melting point. The energy transfer mechanism is mainly radiation from the arc and conduction between the heated refractories and the charge. The furnace rotates during heating of the dross to provide mechanical stirring. The rotation also prevents formation of hot spots on the charge or refractories, and improves energy transfer (Drouet et al., 1995). On completion of heating, the metal is tapped from the furnace through a side tap hole. The solid residues remaining in the furnace form a grayish powder which is removed, as shown, by tilting the furnace forwards while slowly rotating it. Of course no salt is added to the charge and the treatment is done under argon to prevent oxidation of any recoverable aluminum metal.

2.3. The ALUREC process


Using electricity as the source of heat was regarded too complex and expensive by AGA and its partners, Hoogovens Aluminum and MAN GHH. Instead, their efforts were focused on improving the fuel heated rotary furnace technology by using an oxygen-fuel burner and by controlling the atmosphere in the furnace to limit oxidation of the recoverable aluminum metal (Gripenberg et al., 1995, 1997).

Fig. 3. Phases of the DROSCAR process (Drouet et al., 1994, 1995). (a) Dross charging. (b) Heating. (c) Aluminum tapping. (d) Discharging solid residues.

8 nlu N. U , M.G. Drouet / Resources, Conser6ation and Recycling 36 (2002) 61 72

65

Fig. 4. ALUREC process (Drouet et al., 1995).

A rotary tiltable converter type furnace, used for the process called ALUREC, is illustrated in Fig. 4. The oxy-fuel burner and the exhaust gas port are located on the same side. This design offers high-energy efciency and very good possibilities to control the furnace atmosphere (Gripenberg et al., 1995). The oxy-fuel burner heats the converter refractory wall in a short time to about 1000 C. Through furnace rotation, the heat is transferred to the charge by conduction, and the heat is further distributed within the charge by mixing. Heat is also transferred through direct radiation from the ame to the charge (Gripenberg et al., 1995). The metal is collected at the bottom of the converter, and the solid NMP oats on top. The metal is tapped separately from the NMP, it can be returned directly into the melting or holding furnaces or is cast into sows or T-ingots. The NMP is discharged through the converter mouth (Gripenberg et al., 1995).

2.4. The ECOCENT process


ECOCENT is an economical and ecological aluminum recycling process where by some of the metal contained in the dross is recovered by centrifuging the hot dross (Fig. 5). ECOCENT, developed by FOCON in Austria, is based on the idea of treating the hot dross as quickly as possible in a single operation to avoid exothermic losses, intermediate storage and unnecessary handling as well as to save energy. In the ECOCENT process the hot dross is fed without any uxing salt additions into a converter where the relevant parameters for separation like temperature and viscosity can be adjusted. In addition, big lumps of dross are crushed into smaller pieces in order to improve the later separation of the metal. After homogenizing and adjusting the temperature the hot dross is poured as quickly as possible into a centrifuge. In the ladle or alternatively in the mould of the centrifuge the centrifugal forces are used for the separation of the metal from the aluminum oxide, the major constituents of the dross. As soon as the centrifuging is nished the liquid aluminum can be poured back into the furnace or can be used

66

8 nlu N. U , M.G. Drouet / Resources, Conser6ation and Recycling 36 (2002) 61 72

for ingot pouring. After the pouring of the metal the dry residues are removed just by tilting the ladle. Alternatively, the aluminum solidies in the mould and is discharged as a compact ring. The separation of the residues from the aluminum ring is automatic (Kos, 1997, 2000).

2.5. PyroGenesis DROSRITE process


The DROSRITE process, developed by PyroGenesis, is an other salt-free dross processing technology. With DROSRITE, hot dross is charged to a refractory-lined rotary furnace, immediately after skimming from the aluminum holding furnace. The DROSRITE furnace is sealed and maintained under an argon atmosphere. The furnace is rotated, as it is necessary to gently tumble the charge, for roughly 15 30 min. The tap hole is opened, and the metal is poured into the receiving vessel or ladle. A controlled amount of oxygen is then injected into the furnace cavity, burning some of the non-recoverable aluminum metal contained in the residue. When the temperature reaches the target value, typically in the range of 800 900 C, oxygen injection is stopped. Purging with argon is repeated before discharging the residues. DROSRITE residues are particularly clean (Drouet et al., 2000).

3. The comparison of the salt-free dross processing methods The technologies, just described, have been characterized by their different operating conditions such as the nature of the heating source, the furnace atmosphere, the type of dross treated, hot or/and cold, the type of treatment vessel, in one case the presence of cooling water, etc. The technologies are also characterized by different metal recovery, composition of the treatment residues and treatment cost. A comparative analysis of these last characteristics will now be presented. The energy efciency of air plasma being somewhat higher than that of the nitrogen plasma, and since nitrogen is more expensive, air plasma is preferred and

Fig. 5. Ecocent process standard procedure (Kos, 1997, 2000).

8 nlu N. U , M.G. Drouet / Resources, Conser6ation and Recycling 36 (2002) 61 72

67

Fig. 6. PyroGenesis DROSRITE process (Drouet et al., 2000).

used in the ALCAN process. The energy efciency is reported to be as high as 80 95% (Lavoie and Dube, 1991). In Fig. 6 the typical energy origin and utilization are given for the two different heating methods using a plasma torch and an arc (Drouet et al., 1994). The energy input may also come from the nitridation and oxidation of the metal in addition to that coming from the burner or the electrical torch or arc. Losses are through the walls, the door when open, the stack, and also in the torch cooling water. The oxidation and nitridation of the aluminum by the air plasma is an important source of heat (28% as indicated in Fig. 6a). This reduces recovery of aluminum by 5% (Fig. 7a) and increases the amount of residues by 8%. However, using recoverable aluminum metal as a fuel to heat the furnace is not economical and should be avoided if possible. Furthermore, in the plasma torch process, the necessity to periodically remove the torch from the furnace for electrode maintenance requires highly specialized torch maintenance personnel (Drouet et al., 1994). By contrast, the graphite arc technology proposed by Hydro-Quebec does not use any cooling water and maintenance is not intensive as is the case for the plasma torch technology. Furthermore, gaseous and particulate emission are signicantly reduced with the DROSCAR technology which requires only 3 m3 of gas per ton of dross treated, compared to 30 m3/ton dross for the air plasma torch and as much as 300 m3/ton for the gas or fuel burner. Argon is used especially for arc stabilization, but its properties help to create an inert atmosphere inside the furnace signicantly reducing any reaction between the molten aluminum and the furnace atmosphere. As the process uses a graphite arc, there is no water-cooled part in the DROSCAR furnace, thus the hazard created by possible water-leaks over the molten metal has been eliminated. The total cycle time to treat 1 ton of aluminum dross at the 600 kW pilot plant has been reduced to 65 min. This includes the time for charging and heating, aluminum tapping and residue discharging. In the

68

8 nlu N. U , M.G. Drouet / Resources, Conser6ation and Recycling 36 (2002) 61 72

Fig. 7. Energy sources and utilization per ton of dross input containing 50wt% free aluminum (Drouet et al., 1994). (a) Air plasma torch process. (b) Graphite electrodes process.

DROSCAR, no metal combustion occurs. The average electrode consumption measured is 0.91 kg per ton of dross. Since the DROSCAR process is operated under an inert atmosphere without salt addition, the residues are less contaminated than those produced by an air plasma torch or a fuel burner (Drouet et al., 1995) (Fig. 8).

Fig. 8. Mass balance per ton of dross input containing 50wt% free aluminum (Drouet et al., 1994). (a) Air plasma torch process. (b) Graphite electrodes process.

8 nlu N. U , M.G. Drouet / Resources, Conser6ation and Recycling 36 (2002) 61 72

69

In the ALUREC process, the exhaust gas from the oxy-fuel burner does not contain nitrogen. By contrast, air fuel burners and plasma burners (air or nitrogen based) produce exhaust gases with high concentrations of nitrogen. The presence of nitrogen in the ame provides a potential for the formation of aluminum nitrides that would contaminate the by-product from the process and could affect the aluminum yield. Furthermore, the presence of nitrogen in the air plasma also promotes the formation of NOx, which is not the case with ALUREC where no nitrogen is used. The volume of exhaust gas from an oxy-fuel burner is small, only about 25% of that of an air fuel burner. This results in a smaller ame, and direct contact with the charge can be avoided. There will be less convection and less mass transfer between the oxy-fuel ame and the charge. Furthermore, the thermal efciency of an oxy-fuel heated furnace is much higher due to the small exhaust gas volume. Considering the small exhaust gas volume, the exhaust gas composition and possibilities of accurately controlling this composition with oxy-fuel, it was concluded that the aluminum oxidation in the process would be under control. While the RSF process uses a salt ux, ALUREC uses atmosphere control to prevent oxidation (Gripenberg et al., 1995) and therefore no salt addition is required. The reduced exhaust gas volume in combination with the increased ame temperature results in a more energy efcient process. Compared with air fuel, the energy consumption will be lower with oxy-fuel. The emissions of CO2 and SO2 will be reduced, since they are proportional to the fuel consumption. The formation of NOx is reduced because nitrogen is excluded from the combustion process. Depending on dross composition, about 500 kg of NMP is produced for each metric ton of dross. This is about half the amount of by-product compared with the RSF process. From the comparable tests, the metal recovery, dened as metal cast/dross charged, was between 45 60% with fuel consumption in the range of 200 400 kWh per ton of dross (Gripenberg et al., 1995). With ECOCENT, the consumption of the energy is more than 50% lower compared to conventional dross processing technologies as the ECOCENT process is using the inherent energy of the hot dross and no heating or uxing salt is needed. The high recovery rate and the pure metal result in a short amortization period. The electronically controlled process needs no cooling water and is simple, safe and environmentally sound (Kos, 1997). The novel process developed by PyroGenesis, named DROSRITE, does not require any external energy input either. Process energy is extracted from the solid residue, stored in the furnace refractory wall, and released to the next batch of fresh dross. Furthermore, the process is operated online with the molten aluminum holding furnace where the dross is generated. Thus, the hot metal can be returned to the furnace immediately after tapping still in its molten form. Energy savings in comparison with conventional processes can exceed 2.500 kWh/ton of dross. The recovery rate with DROSRITE was found to be 10% more than with RSF. The actual recovery with any process will of course depends on the initial metal content in the dross. Mass and energy balances for such a 2.1 ton DROSRITE unit are presented in Figs. 9 and 10, respectively, with the assumption that the process will,

70

8 nlu N. U , M.G. Drouet / Resources, Conser6ation and Recycling 36 (2002) 61 72

Fig. 9. Mass balance for a 2.1 ton DROSRITE unit (Drouet et al., 2000).

8 nlu N. U , M.G. Drouet / Resources, Conser6ation and Recycling 36 (2002) 61 72

71

Fig. 10. Energy balance for a 2.1 ton DROSRITE unit (Drouet et al., 2000).

in this example, recover 600 kg of aluminum from each ton of dross. Environmental advantages are even more marked. There is no salt cake requiring disposal. No carbon dioxide or NOx gases are produced. No nitrides are formed. The process has little off-gas and produces a residue that is suitable for the production of calcium aluminate or for other value-added use (Drouet et al., 2000).

4. Conclusions In the past, aluminum dross has constituted an unwanted by-product which was to be eliminated in a quick and economic way. To remove the environmental and nancial disadvantages of the traditional rotary salt furnace process, several dross treatment technologies have been developed during the last 10 years by the aluminum industry. By the elimination of the need for salt ux, the energy consumption is minimized, a high metal yield, reduced ue gas volume and emissions are obtained, and an environmentally sound non-metallic by-product is produced which can be recycled.

References
Drouet MG, Handeld M, Meunier J, Laamme CB. Dross treatment in a rotary arc furnace with graphite electrode. J Metals 1994;5:26 7.

72

8 nlu N. U , M.G. Drouet / Resources, Conser6ation and Recycling 36 (2002) 61 72

Drouet MG, Meunier J, Laamme CB, Handeld MD, Biscaro A, Lemire C. A rotary arc furnace for aluminium dross processing. In: Quenean PB, Peterson RD (editors). Third International Symposium on Recycling of Metals and Engineered Materials, 12 15 November 1995, Point Clear, Alabama. The Mineral, Metals and Materials Society; 1995. p. 803 12. Drouet MG, Leroy RL, Tsantrizos PG. Drosrite salt-free processing of hot aluminium dross. In: Stewart DL, Daley JC, Stephens RL (editors). 2000 TMS Fall Extraction and Process, Metallurgy Meeting, 22 25 October 2000, Pittsburgh, Pennsylvania. The Minerals, Metals and Materials Society; 2000. p. 1135 45. Gripenberg H, Grab H, Flesch G, Mullerthann M. Alurec a new salt-free process. In: Quenean PB, Peterson RD (editors). Third International Symposium on Recycling of Metals and Engineered Materials, 12 15 November 1995, Point Clear, Alabama. The Mineral, Metals and Materials Society; 1995. p. 819 28. Gripenberg H, Mullerthann M, Jager N. Salt-free dross processing with Alurec two years experience. Light Metals 1997:1171 5. Kos B. A new concept for direct dross treatment by centrifuging of hot dross in compact type ecocent machines. Light Metals 1997:1167 9. Kos B. Direct dross treatment by centrifuging of hot dross. Aluminium 2000;76:35 6. Lavoie S, Dube G. A salt-free treatment of aluminium dross using plasma heating. J Metals 1991;2:54 5. MFS Engineering Ltd Catalogs. Rotary Dross Cooling Systems. Switzerland: Kreuzlingen; 1997. p. 1 6. Ruff WS. From waste to valuable raw material renement of aluminium dross. Aluminium 1998;74:1 2.

Anda mungkin juga menyukai