Use of Microwave energy in Metallurgy

D. Panias, A. Krestou
National Technical University of Athens- School of Mining and Metallurgical Engineering, 9, Heroon Politechniou Street, Zografos Campus, 15780 Athens, Greece

ABSTRACT Microwaves have been extensively used over the past thirty years in domestic applications. The use of microwave energy in materials processing is a rather new development presenting numerous advantages which result from the rapid heating throughout the materials. The prompt increase of temperature in the bulk of the materials is the consequence of their penetration by the microwaves with subsequent vibrations of the polar molecules and production of energy in the form of heat. The use of microwaves in metallurgy is in early stage. Although microwave energy hasnt been applied extensively in metallurgical processes, it presents a lot of advantages including the rapid completion of the processes, high yields, low operating and capital costs, environmental benefits etc. In the present paper a review on the utilization of microwave energy in metallurgical processes is presented, with a simultaneous comparison with the corresponding traditional methods. 1. INTRODUCTION Microwave energy is a non-ionizing electromagnetic energy characterized by mutually perpendicular electric and magnetic fields (Kuslu and Bayramoglu, 2002). Microwaves occupy the part of the electromagnetic spectrum from 300MHz (3x108 cycles/s) to 300GHz (3x1011 cycles/s), (Com. on Microwave proc. Mat., 1994). The two frequencies reserved by the Federal Communications Commission (FCC) for microwave heating in industrial, scientific and medical (ISM) applications are 0.915 and 2.45GHz (Thostenson and Chou, 1999). Microwaves were first used during the World War II in radar systems, while their usefulness in the heating of materials was discovered in 1946. However, the likelihood of the radiofrequency utilization in the heating of materials was forecasted in 1943, when engineers working on short- wave transmitters contracted artificial fevers (Com. on Microwave proc. Mat., 1994). For commercial applications, the first microwave oven was developed in 1951 when a large floor standing model was produced by the Reython Company in North America. (Kingman and Rowson, 1998). The massive use of microwaves in thermal processing lays in the way the materials are heated. In contrast to conventional heating, microwave energy is delivered directly to the material through molecular interaction with the electromagnetic field (Thostenson and Chou, 1999). This difference in the way energy is delivered can result in many potential advantages to using microwaves for the processing of materials, such as uniform heating of complex shaped materials, effective heating of materials with low conductivity (Clark et al, 2000), selective heating of distinct phases that couple with microwaves (Thostenson and Chou, 1999) etc. Additionally, the associated apparatus need not be heated, resulting in cooler working conditions for people who work with the equipment (Clark et al, 2000). The main drawback of the use of microwave energy in processing materials is the difficulty in achieving repeatability of measurements,

since the results can be affected by a myriad of issues, such as moisture content, changes in dielectric properties during processing, electromagnetic interference with temperature measurements, sample size and geometry, or placement of the sample within the cavity (Com. on Microwave proc. Mat., 1994). However, the plethora of advantages that microwave energy provides could result in the substitution of many conventional industrial applications by more sophisticated ones, in which microwaves comprise the main energy resource. During the last years an extensive research has been conducted concerning the use of microwaves in metallurgical applications. The present work gives a review of this research and at the same time compares the corresponding conventional method with the one that introduces the use of microwave energy. 2. FUNDAMENTALS OF MICROWAVES 2.1 Interaction of electric field with materials The response of materials upon exposure to electric field is strongly affected by their dielectric properties. In conductors, electrons move freely in response to the electric field resulting in an electric current. The flow of electrons heats the material through resistive heating, unless the material is a superconductor. However, metallic conductors largely reflect microwaves, thus they are not heated effectively. Dielectrics are the materials that are easily heated by microwaves (Haque, 1999). When the field change occurs near the natural frequency where reorientation happens, a maximum in energy consumption is realized and optimum heating takes place. When this is happening, the material is said to be well coupled. Materials that are transparent to microwaves are classed as insulators (Com. on Microwave proc. Mat., 1994). 2.2 Material properties The most important properties that dominate the heating of materials by microwaves are the complex permittivity, *, and the loss tangent, tan (equations 1 and 2, respectively).

tan =

eff r

(2)

where, : is the real permittivity (a function of temperature and frequency) characterizing the penetration of microwaves into the material, : is the loss factor indicative of the materials ability to store energy, 0: is the permittivity of free space, r: is the relative dielectric constant, eff: is the relative dielectric loss factor, tan: indicates the materials ability to convert absorbed energy into heat. Materials with high are considered reflectors wile materials with low are transparent to microwave energy (Thostenson and Chou, 1999). 2.3 Energy conversion The combination of the dielectric properties of a material and the frequency of the applied electromagnetic field control the heating of the material. Therefore, the effectiveness of microwave heating is the result of the extent that the microwave energy is absorbed by the material exposed to the electromagnetic field. The majority of the absorbed microwave power is converted to heat within the material, as described in Equation 3, (Clark et al, 2000):
2 f 0 eff = C p t
2

(3)

where, T: temperature, t: time, f: microwave frequency, E: magnitude of the electric field, : density, Cp: heat capacity. 3. METALLURGY AND MICROWAVES The energy problem raised by the oil and gas storage in the mid 1970s, led many researchers in the development of energy preserving technologies, including the use of microwaves, especially in the minerals processing field. In

) * = i = 0 g( r eff

(1)

1978, Zavitsanos obtained a U.S. patent for the desulphurization of coal using microwaves. This was the first recorded attempt to expose minerals to microwave radiation (Kingman and Rowson, 1998). 3.1 Minerals Processing Since the beginning of the 20th century the beneficial results of thermal pretreatment of minerals was known (Yates, 1918-1919). Although grinding resistance of the minerals seemed to be considerable reduced upon thermal pretreatment, the overall process was economically unfavorable. In 1991, Walkiewicz et al, considered the use of microwave energy in thermal pretreatment of iron ore samples. Their results showed that the microwave radiation reduced the work index of the iron ores by between 10 and 24%, resulting in less wear of the mill, the mill liner and the milling medium. Improved grindability also resulted in an increased throughput and a reduction of the amount of any recycled ore. Vorster et al (2001) studied the effect of microwave energy on the grindability of a massive copper ore (MC) and a massive copper zinc sulphide ore (MCZ). The results of their study showed that after 90 seconds exposure, a reduction in work index of the MC-ore reaches 70%, while the work index of the MCZ-ore under the same exposure to the microwaves reduced to only 50% for nonquenched samples and 65% for water quenched samples. The benefits of microwave energy in the grinding of ores are a consequence of the selective heating of distinct phases within the ore, resulting in thermomechanical stresses within the treated mineral (Jones et al, 2002). However, thermally assisted grinding using microwave radiation is most effective when the microwave absorbing mineral (metal oxides, carbon, sulphide ores, arsenides etc) is contained within a transparent gangue (silicates, carbonates, sulphates and some oxides), (Kingman et al, 1999). Microwaves have been also studied in a laboratory scale for the regeneration of granular activated carbon used in modern gold refractory techniques (carbon-in-pulp process, CIP). The laboratory scale experiments showed that microwave regeneration of the loaded carbon resulting from this process can give activated

carbon which performs well or better than conventionally regenerated carbon and can be re-used in the process (Bradshaw et al, 1998). A preliminary economic assessment concluded that the microwave regeneration of the loaded carbon yields a return on investment of 12%. Currently, Ontario Hydro, Toronto, Ontario, Canada is marketing this technology (Haque, 1999). 3.2 Pyrometallurgy Standish and Worner (1996) considered the applications of microwave energy for the reductions of metal oxides with carbon, i.e. ironmaking. In their experiments they used identical samples of hematite ore fines, coke dust and lime powder, some of which reduced conventionally at 1000C and others in a microwave oven at 1.3kW with a frequency of 2.45GHz. The results obtained showed that microwave heating resulted in a 16% increase of weight loss over conventional heating, while no cold centers occurred in the treated ore. Microwave energy has been found to be advantageous in the reduction of pre-oxidised Ilmenite concentrates (Kelly and Rowson, 1995). Ilmenite concentrates were oxidized in conventional muffle furnace at 1000C and the ferric iron was then reduced back to ferrous iron either by conventional heating at temperatures between 700-1000C, or by microwave heating at variable power (0-1500kW) with a frequency of 2.45GHz. The outcomes of this work were that almost total reduction of ferric iron can be achieved in very short period of time by exposing the samples at microwave radiation (typically 8mins at 750W compared to 8hrs at 800C), while, in microwave reduced samples, the higher the extent of reduction the better the extraction of iron. As far as the dissolution characteristics are concerned, these seemed to be similar for both reduction pathways. Pyrometallurgical technologies have been widely applied to liberate gold particles from refractory gold ores. Many researchers have considered the application of microwave energy to the extraction of gold either as a pretreatment or during the conventional processing techniques (Woodcock et al, 1989). A work by Haque (Haque, 1987) showed that microwave energy was highly effective in the calcination of

the concentrate, when the particles were 2mm in diameter or lower. The advantages that microwave treatment offered over the conventional calcination were the low roasting temperature (500C) and the high yield of the gold extraction (98%) after cyanidation of the resultant calcine. The main drawback was the volatisation of more than 80% of the arsenic and sulphur as As2O3 and SO3, respectively, and the oxidization of iron to hematite at 550C. The same author also conducted experiments where the same concentrate was mixed with NaOH and exposed to microwave heating. The results of these experiments showed that the formation of As2O3 and SO3 is avoided and instead water soluble products are formed (Na3AsO4, Na2SO4, FeSO4). Microwave energy can be also utilized for the desulphurization of coals with removal of sulphur either as elemental sulphur or pyrite (Jones et al, 2002). Many researchers (Agarwal et al, 1975, Butcher and Rowson, 1995) showed that at 2.45GHz pyrite heats more rapidly than coal and this heating has the effect of enhancing the magnetic susceptibility of pyrite improving the removal rates by magnetic separation. Following the work by Butcher and Rowson, Lovs et al (2003), studied the intensification of the magnetic separation of chalcopyrite (CuFeS2) and tetrahedrite from Cu-ores using microwave radiation. Microwave heating causes phase changes of sulphides and in consequence of their thermic decomposition, changes in magnetic properties occur (Lovs et al, 2003). The experiments carried out in the work of Lovs et al, showed a rapid decomposition of CuFeS2 to maghemite (- Fe2O3), which presents a magnetic susceptibility 100 times higher than the one of CuFeS2, while the time needed for the same decomposition with conventional heating is substantially higher. The results also indicated that a rise in the time of microwave radiation from 20 to 30 seconds increased sharply the magnetic susceptibility in the order of 300 to 980%, depending on the grain size of the samples. Similar results were obtained for tetrahedrite, where the magnetic phase that was formed in only few minutes was cuprospinel- CuFe2O4. The microwave assisted decomposition of tetrahedrite resulted in the release of volatile substances (Hg, Sb and As). However, this drawback could be diminished

with the presence of activated coal during heating. The rapid decomposition of considerable portions of CuFeS2 and tetrahedrite with little energy consumption was not the only advantage of the use of microwaves. The rise of the magnetic properties of the formed phases made their separation from the copper ore easier, and therefore decreased the required energy. 3.3 Hydrometallurgy The exposure of zinc silicate ores (hemimorphite, Zn4Si2O7(OH)2H2O) in microwave radiation for the extraction of zinc has been considered as a fundamental study by Hua et al (2002). In the hydrometallurgical processes already applied, filtration problems arise due the formation of silica gel. Many researches (Ikenobu, 2002, Perry, 1966, Mattwew and Elsner, 1977) have overcome the difficulty of filtration but they have initiated other problems (complicated methods, operating parameters must be properly controlled, high iron dissolution). The work of Hua et al (2002) showed that, when microwave irradiation is used there is a reduction of energy consumption since the reactions can proceed at low temperatures (below 176C). Additionally, the extraction of zinc reaches 98.27%, more filterable silica is produced while the percentage of dissolved iron is very low (0.1%). The use of microwave energy for the extraction of zinc from electric arc furnace (EAF) dust, which is a hazardous by-product generated by the melting of scrap steel in an electric arc furnace, has been also considered (Xia and Pickles, 2000). With the microwave caustic leaching of the EAF dust a recovery of zinc in the order of 80% was reached in only five minutes when with the conventional leaching the maximum recovery was 72% and was reached in more than one hour (180 minutes). The research indicated that higher dissolution rates could be reached at higher power levels, while no stirring was required since the leaching reactions in the microwave oven were very violent. The high yield and the rapid leaching were not the only advantages of the microwave alternative method introduced by this work (Xia and Pickles, 2000). In contrast to the conventional leaching, in the microwave

method less caustic solutions can be used while for a given leaching time more zinc is dissolved than lead. Copper sulfation is a hydrometallurgical alternative to the present smelting practice that generally produces significant amounts of contaminant gases and therefore demands high cost installations for environmental preservation (Yianatos and Antonnucci, 2001). For copper minerals leaching, microwaves provide rapid heating and are particularly reactive for chalcopyrite, which is the main contaminant in molybdenite concentrates (Chen et al, 1984). The study of the leaching of a molybdenite concentrate with sulphuric acid using microwave assisted copper leaching was studied by Yianatos and Antonucci (2001) in a batchtype process. The findings of their research included the reduction of the copper content of the molybdenite concentrate from 3.6% to less than 0.1% (higher than 95% sulfurization) in less than 15 minutes at temperatures between 190 and 240C, as well as minimum molybdenite and pyrite dissolution. The specific energy consumption was about 0.9MWh/ton, whereas the conventional smelting process demands less energy. However, the production of elemental sulfur under controlled conditions was advantageous (Antonucci and Correa, 1995). The work by Yianatos and Antonucci (2001) also showed that the sulfation of the molybdenite ore could be completed much more rapidly by increasing the power supply level, however there were restrictions of gas transport and local ignition. The effect that microwave radiation has on the dissolution of pyrite has been studied on a laboratory scale by Kuslu and Bayaramoglu (2002). In their experiments they used pyrite samples obtained form a copper industry in Turkey, which contained 46.35% Fe, 47.52% S and 2.4% SiO2, with pyrite content being equal to 88.9%. The leaching solutions used were acidic ferric sulphate solutions with concentrations of H2SO4 and Fe3+ both varying from 0.5 to 2N, while the microwave frequency was 2.45GHz. The experiments were conducted at a temperature range between 50 and 80C and the results indicated that the use of microwaves increases the dissolution rates of pyrites. An interesting finding of this work was the fact that microwave radiation does not affect the reaction

mechanism of the pyrite dissolution in acidic ferric sulfate solutions. However, the activation energy when microwaves are used is equal to 18.72KJ/ mol and almost half of the one needed when conventional heating is applied (33.43 KJ/ mol). The influence of microwave radiation at leaching of chalcopyrite concentrate, CuFeS2, has been also studied (Lovs et al, 2003). The results indicated that desirable yields of utility components could be achieved in less than an hour leaching of chalcopyrite in Fe2(SO4) or FeCl3 media, in contrast to currently known methods that cannot ensure the same yields and are time and energy consuming. It was also concluded that ferric chloride is preferable for the leaching of chalcopyrite at 90C when microwave heating is applied, while the ferric sulphate solution becomes effective only if the temperature of the leaching suspension exceeds 100C. Research concerning the use of microwaves for the pre- treatment of refractory gold ores has been also carried out (Huang and Rowson, 2002) as an attempt to develop currently conventional hydrometallurgical methods that are commonly applied and use nitric acid solution as oxidant. In their work, Huang and Rowson (2002) studied the decomposition of pyrite and marcansite in a nitric acid medium. The results of this study showed that microwave energy lowers the decomposing time to only 10 minutes when high enough concentrations of HNO3 (4M) are used and temperature is in the range of 90 to 110C. Under the aforementioned conditions, 93% of pyrite and almost all of the marcansite were decomposed. Heating by electric energy under identical conditions gave average decomposition rates of pyrite and marcansite approximately 5-20% lower, however no deviations in the activation energy were observed (Huang, 2000). Finally, microwave energy failed to diminish the formation of elemental sulphur or to dissolve the formed elemental sulphur, which is detrimental to the recovery of gold from refractory gold ores and concentrates. 4. CONCLUSIONS The application of microwave heating on many metallurgical processes on a laboratory scale,

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