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By Masao Suzuki

Over 5 million cars are scrapped yearly in Japan. After dismantling. scrapped automobiles, they are put into a shredder for differential recovery of ferrous and nonferrous metals. The residue, which is called shredder dust, runs over 1.2 million tons per year. This paper reports a entire sequence of scrapping. cars. in Japan with the following sections: (1) production and scrapped car management, (2) material composition, (3) dismantling, (4) shredder plant, (5) differential recovery of metals including specific gravity separation and newly developed color separation.

Jan 1, 1995

By Selim Coskun

In this study, tungsten matrix composites reinforced with 2 wt% TiC particles were mechanically alloyed (MA?d) for 3h, 6h, 12h and 24h. 1 wt% Ni is used as sintering aid which is added before and after mechanical alloying. Microstructural and phase characterizations of composite powders and sintered samples were carried out via SEM and XRD analyses. Furthermore, density and hardness measurements of as-consolidated and sintered samples were carried out. Additionally, DSC experiments were conducted to investigate the sintering behavior of the MA?d powders.

Jan 1, 2009

By Filippos Patsiogiannis

Laboratory size (4.5 kg) low carbon steel melts were deoxidized using Al and FeAl (33% Al), with and without synthetic fluxes, in alumina and zirconia crucibles. The dissolved oxygen, total oxygen, soluble aluminum, insoluble aluminum, silicon and carbon contents in the melt were determined as a function of refining time and temperature. It was observed that the reaction between aluminum and oxygen in solution closely follows thermodynamic equilibrium. Silica present in the alumina crucibles was found to be a source of oxygen for the melt, while this was not the case for zirconia crucibles. Reoxidation of the melt occurred through oxygen pick-up from the atmosphere. The extent of this reoxidation was found to be a function of oxygen content of the bath and the slag cover on the surface of the melt. The effectiveness of calcium-aluminate based fluxes in protecting the melt from the reoxidation and in increasing the rate of removal of inclusions was evaluated.

Jan 1, 1992

By J. Gartelmann, B. Zaslavsky, Y. Vojta, D. J. Chaiko, W. Mego, A. N. Rollins

"Aqueous biphasic extraction (ABE) processes offer the potential for low-cost, highly selective separations. This countercurrent extraction technique involves selective partitioning of either dissolved solutes or ultrafine particulates between two immiscible aqueous phases. The extraction systems that we have studied are generated by combining an aqueous salt solution with an aqueous polymer solution.We have examined a wide range of applications for ABE, including the treatment of solid and liquid nuclear wastes, decontamination of soils, and processing of mineral ores. We have also conducted fundamental studies of solution microstructure using small angle neutron scattering (SANS). In this chapter we review the physicochemical fundamentals of aqueous biphase formation and discuss the development and scaleup of ABE processes for environmental remediation.IntroductionAqueous biphasic extraction (ABE) is a highly adaptable separation technique that can be used in a wide range of applications. We have been evaluating various types of ABE systems for possible applications in the treatment of solid radioactive wastes (1,2), liquid nuclear wastes (3,4), and contaminated soils (5-7), and in the removal of organics from aqueous salt solutions (8). We have also conducted fundamental studies of the solution microstructure of ABE systems using small angle neutron scattering (SANS) (9).The extraction systems are generated by combining an aqueous salt solution and an aqueous polymer solution. This produces two distinct liquid layers that are as immiscible as oil and water, yet each liquid layer contains at least 70 to 80 wt % water. The biphasic systems that we have been working with consist of immiscible polyethylene glycol (PEG) and salt solutions. Some inorganic salts that promote biphase formation with PEG solutions include the sodium/potassium salts of sulfate, carbonate, phosphate, and hydroxide (10)."

Jan 1, 1996

By Anja Pfennig, Thomas Böllinghaus, Marcus Wolf

During CCS components are exposed to a corrosive environment and mechanical stress which results in corrosion fatigue and is inevitably followed by the lifetime reduction of these components. The lifetime reduction of the cyclically loaded high alloyed stainless injectionpipe steel AISI 420C (X46Cr13, 1.4034) constantly exposed to highly corrosive CO2- saturated hot thermal water is demonstrated in in-situ-laboratory experiments (T = 60 °C, brine: Stuttgart Aquifer, flow rate: 30 l/h, CO2) in an environment similar to the on-shore CCS-site in the Northern German Bassin. In-situ tension-compression experiments were established simultaneously along with electrochemical measurements using a newly designed corrosion chamber in a resonant testing machine at a frequency as low as 30 – 40 Hz. In addition technical CO2 was introduced into the closed system at a rate close to 9 L/h. S-N plots, micrographic analysis and surface analysis of the fracture surface are demonstrated. X46Cr13 (surface roughness Rz = 4) reached the maximum number of cycles (12.5 x 106) at stress amplitude of 173 MPa producing a low scatter range of 1:3.5. Hydroxide and siderite layers were found on pits and crack surfaces. No typical fatigue limit exists. Pit corrosion prior to crack initiation may be identified as failure cause.

Jan 1, 2016

By Peng Jianping, Feng Naixiang, Di Yuezhong, Wang Yaowu, Pan Xijuan

A vacuum silicon thermal reduction lithium process is developed in present work which used lithium hydroxide, alumina and calcium oxide as raw materials. The process contains two steps, which are that Li5AlO4 clinker is prepared in ambient environment, and that metal lithium is extracted from Li5AlO4 clinker with ferro-silicon alloy as reductant in vacuum. On the basis of thermodynamic analysis and investigative experiments, feasibility of this process is proved. The results show that Li5AlO4 can be generated by calcination lithium hydroxide and alumina, the burning loss is above 31% under the conditions of calicination temperature above 750℃ and time more than 90min. The main phases of calcination product are Li5AlO4 and CaO. When the calcination product is reduced by ferro-silicon alloy in vacuum, the lithium reduction ratio can be over 80% under the conditions of reduction temperature 1200℃ and reduction time 60min.

Jan 1, 2014

By Tibor Zoltai

Asbestos is a generic term for industrially useful fibers recovered from exploitable deposits of the asbestiform varieties of five silicate minerals: chrysotile, anthophyllite, actinolite-tremolite, cummingtonite-grunerite, and riebeckite. Asbestos and asbestiformm fibers of some other minerals are known to be carcinogenic. Minerals crystallized in the asbestiform habit are characterized by unique properties (morphology, strength and flexibility, physical and chemical durability, and defect-free surface structures). The key to the unusual properties, and health effects, of asbestifarm fibers appears to be in their unusual surface structure. In contrast, non-asbestiform crystals of the same minerals, including the five so-called asbestos minerals do not have these properties and are not carcinogenic (1, 2).

Jan 1, 1989

By N. L. Piret

In copper smelting minimization of solid waste generation is receiving increased attention with more stringent environmental legislation and lower disposal space availability. Copper smelting slags generally being valorizable, solid waste generation is attributed to the presence in the feed of unvalorizable impurities which do not report to the slag and to the unavoidable formation of contaminated dilute acid solutions which need neutralization. As to unvalorizable impurities, solid waste minimization is achieved by rejecting them in the highest possible concentration. Dilute acid is mainly due to the formation of SO3 in the smelter gases and to the discard of decopperized bleed-off electrolyte. Its generation is substantially lowered by preventing SO3 formation, by converting the dilute acid to a valorizable product, e.g., by thermal decomposition for H2S04 recovery or by precipitation as chemical gypsum, and by suitable treatment of the bleed-off electrolyte for impurity removal. Industrial processes are evaluated and alternatives are discussed.

Jan 1, 1994

By Chen-Ming Kuo, Esher Hsu

"The importers and manufacturers who import or produce products with packaging containers are charged a recycling fee in Taiwan. The amount of waste packaging containers used for calculating the recycling charge is based upon the amount declared by importers and manufacturers which might be underestimated. This study aims to estimate the amount of waste packaging containers generated by households in Taiwan and also explores its distribution. The sampling survey and ratio estimation are conducted for estimating the recycled amount; while the refuse sampling method for municipal solid waste composition is employed to estimate the un-recycled waste packaging containers. The estimated total amount of waste packaging containers in 2011 generated by households in Taiwan is 696,511 m.t., of which, 79.49% of the waste packaging containers were recycled and 20.51 % were landfilled or incinerated. This study shows that the amount of waste packaging containers declared by importers and producers is underestimated around 20%.IntroductionWaste packaging containers including iron cans, aluminum cans, glass bottles, plastic containers, paper containers, aluminum foiled paper packs are officially announced to be recycled in Taiwan. In order to create the economic incentive for raising recycling performance, associated manufacturers and importers are charged a recycling fee to subsidize recyclers. The amount of packaging containers declared by importers and manufacturers is used for calculating the recycling charge and recycling rate. The importers and manufacturers might underreport their producing (importing) amount to pay less recycling fees. Therefore, the estimated waste packaging containers based upon the amount declared by importers and manufacturers is usually underestimated. Related previous studies about waste packaging containers recycling in Taiwan are done by Hsu and co-workers [1-4]. Hsu and Kuo [1] estimated total production values of recycling and evaluated the performance of recycling performance based upon the estimated production values. Hsu and Liu [5] provided a cost analysis of recycling for waste packaging containers in Taiwan. Bor, Chien, and Hsu [2] presented a market-incentive recycling system for waste packaging containers in Taiwan. Hsu and Kuo [4] provided an amending mechanism for product charge and recycling subsidy in response to the social economic changes for waste packaging containers recycling. Lee and Hsu [ 6, 7] explored the distribution, fee rates, and collection rate of waste containers. This study aims to estimate the amount of waste packaging containers generated by households in Taiwan and also explore its distribution."

Jan 1, 2014

By W. H. (Bill) Jay

The destruction of cyanide creates a significant impost on the financial returns of gold mines. These losses increase substantially when ores containing cyanide-soluble copper are treated. Failure to remove or destroy free or WAD cyanide before it is discharged into tailings dams has, on a number of occasions, led to significant fish, bird and animal deaths. Thus, the retention of cyanide within the leach circuit and the recovery or removal of stable metal cyanide complexes needs to become standard practice for all gold mining operations. Furthermore, reducing cyanide purchases will minimise the quantity of cyanide transported to the mine site thereby reducing the opportunity for spillage of this chemical. Many different physical and chemical methods have been investigated for the removal of cyanide from process solutions. All cyanide destruction methods create a financial impost on the economic viability of the gold mine. To reduce these costs, the recycle of cyanide and the economic recovery of the metals solubilised by cyanide is of prime importance. The alternative methods currently in use, or under consideration for the treatment of copper cyanide, entail high reagent costs, produce the recovered metal in a contaminated form and require the safe handling of hydrogen cyanide. These processes will be briefly discussed within this report Environmental and financial benefits are enhanced by recent laboratory and pilot plant studies conducted by Oretek Limited. The Oretek CPC process for the recovery of copper and the recycle of cyanide from copper cyanide-containing solutions does not require pH adjustment to the alkaline cyanide leach conditions. Copper ions are coordinated to a water-soluble and/or an organic soluble polychelating agent under alkaline conditions and the cyanide ions are displaced Membrane separation, or phase separation of the polychelated copper from the cyanide ions enables the cyanide ions to be recycled and the copper to be directly electrowon from the polychelating polymer. The polychelating polymer is then recycled. Ion exchange resins and solvent extraction systems which may be incorporated into the above process will also be discussed in detail.

Jan 1, 1998

By L. W. Beckstead

In a conventional zinc refinery plant, zinc concentrates were roasted at 950°C. The calcine was ground and leached in a series of leaching vessels using sulfuric acid. The pH in the first leaching vessel was maintained at 2.5, while the pH of the solution exiting the last vessel was about 5.4. The leached residue typically contained (in percent) 0.1 Ag, 0.2 As, 0.7 Cd, 2 Cu, 15 Fe, 10 Pb, and 15 Zn, and it was classified as hazardous material according to the EP-toxicity test. In order to make the residue non-hazardous, and to recover most of the metal values from the residue, a brine leach process was developed. The process consisted of leaching the zinc leach residue in CaCI, brine solution at pH 2 for 1 hour at 90°C. Silver extraction was about 95 percent, while lead, copper, cadmium, zinc, and iron extractions were about 80, 50, 50, 30, and less than 0.5 percent, respectively. More extreme conditions of acidity could have been used in the leaching stage to increase zinc dissolution, but iron dissolution would have significantly increased which would have complicated subsequent recovery steps. The leached and washed residue passed the EP-toxicity leach test and could be disposed as non-hazardous. Silver, copper, and lead in the leach solution were recovered by zinc cementation, while zinc and cadmium were recovered by sulfide precipitation. The resulting solution can be recycled in the process after magnesium precipitation.

Jan 1, 1993

By Xin Li, Hai-Xing Fang, Bing Xie, Hong-Yi Li

Chromium-containing vanadium slag (V-Cr slag) was obtained by an industrial smelting process of Hongge Ore, which is valuable vanadium-titanium magnetite to extract V and Cr in China. Sodium roasting thermodynamics of V-Cr slag in presence of oxygen were calculated to evaluate the reactivity of chemical compounds. Results showed that the oxidation of FeV2O4 was intensified in presence of Na2CO3 while the oxidation tendency of FeCr2O4 was far lower than that of FeV2O4. It was probably that reactions of impurities including Al2O3, SiO2 and Fe2O3 with Na2CO3 happened and the products can promote the oxidation of vanadium or chromium compounds in lower valence. Based on thermodynamic analysis, a two-step selective extraction process of vanadium and chromium was proposed. Extraction rate of vanadium was 88.6% while 7.0% for chromium in the first extraction step; extraction rate of 90.7% and 95.4% for vanadium and chromium, respectively, were obtained in the second step.

Jan 1, 2014

By Jerome P. Downey

In the thermal treatment of electric arc furnace (EAF) dusts, zinc is reduced, volatilized, and ultimately recovered either as liquid metal in a splash condenser or as solid zinc oxide in bag filters. During the process, the duet's chlorine and fluorine content also enters the gas phase and condenses as dross in the splash condenser or as salts which contaminate the zinc oxide product. Pretreatment of EAF dust by pyrohydrolysis appeared to offer a means of minimizing the duet's halogen content. The primary research objectives were to experimentally verify the technical viability of pyrohydrolysis and delineate the process parameters requisite for efficient halogen removal. To this end, representative EAF duet samples were secured and characterized by x-ray diffraction, scanning electron microscopy, and Mössbauer analyses. Specific- experimentation focused on the response of halogen extraction to variations in temperature, retention time, water vapor partial pressure, and various additives. The experimental results proved that 97 to 99 percent chlorine extraction and 80 to 85 percent fluorine extraction are consistently achieved when EAF dusts are blended with silica and roasted at temperatures of 850°C or greater in a furnace atmosphere of 75% steam (diluted by air). A statistical analysis further established that more than- a single optimal point exists, thus affording flexibility in parameter selection (e.g., by increasing temperature, the necessary retention time and additive concentrations are decreased). The findings substantiate the feasibility of pyrohydrolysis roasting in reducing the chlorine and fluorine in the EAF dust to a level that will obviate industrial concerns about halogen contamination. The end-product of the pyrohydrolysis procedure is a de-halogenated, self-fluxing calcine which can be directly charged to a plasma or flame reactor. The paper includes design parameters and flow diagrams illustrating the pyrohydrolysis process integrated with the plasma and flame reactor technologies.

Jan 1, 1992

Sanes are utilized to make molds for metal castings in the foundry industry. Approximately a half ton of sand is disposed of for each ton of metal cast in this country. The purpose of this investigation was to study and develop a process to separate chromite sand and silica sand from reclaimed sands for a steel foundry. Physical separations were utilized to yield silica and chromite sands with desirable molding properties. Several different separation methods, including electrostatic, magnetic, and various gravitational approaches were examined. Experimental results are presented. A method was developed to separate chromite sand from silica sand after mechanical or thermal reclamation. The reclaimed sands are passed through a rare earth magnetic separator to separate chromite sand and magnetic impurities from non-magnetic silica sand. Chromite sand can be recovered from magnetic silica sand or magnetic impurities very effectively using a wet concentrating table. The applicabilities of the separation methods are discussed.

Jan 1, 1995

By William Petruk

"Heap leaching is a developing technology for recovering native gold and electrum from low grade deposits and from tailings. Recovery depends on permeability of the rock and ore minerals, size of particles in the heap, and ore textures that influence exposure of gold grains to cyanide solutions. These ore textures include gold-bearing veinlets and microveinlets along fractures and microfractures, gold grains in porous minerals and rocks, and gold graim. occurring along grain boundaries of other minerals. On the other hand, small encapsulated gold grains arc not likely tote exposed even with fine grinding. Most gold grains that occtir along grain boundaries of other minerals can be exposed with a moderate to fine grind, but the. resulting material will be too fine-grained to be permeable in a heap. Such finely ground ore, as well as tailings from flotation operations, can however be prepared for heap leaching by agglomerating the material into porous briquettes. Oxidized and weathered zones above. orebodies are frequently amenable to heap leaching because the gold-bearing pyrite and arsenopyrite have become permeable by conversion to porous iron oxides and ferric oxyhydroxides. A review of ore textures in several types of gold deposits suggests that:(1) the gold in vein deposits would gtmerally be amenable to heap leaching of both oxidized ores and fresh non-refractory ores,(2) the gold in Carlin-type deposits and in volcanogenic massive sulfide deposits is not likely to be amenable to heap leaching fresh ore, but oxidized zones above the orebodies are generally amenable to cyanidation, and(3) the gold in porphyry copper-gold deposits and in Witwatersrand-type deposits would likely be amenable to heap leaching of both fresh and oxidized ores but with high cyanide consumption."

Jan 1, 1997

By P. J. Uggowitzer, H. Kaufmann

"New Rheocasting is a novel route of semi-solid casting, in which the globular semi-solid precursor material is produced by controlled cooling of only slightly superheated melts in conventional steel crucibles. The resulting semi-solid slugs are placed into the sleeve of a vertical Squeeze Casting Machine and then filled into steel dies. Solidification occurs under hydraulic pressures up to 100 MPa Due to the reduced cost of precursor material, reduced investment cost and easier recycling, the New Rheocasting process offers cost reductions of up to 25% over conventional semi-solid casting · routes. The New Rheocast products are pore free, pressure tight, weldable and heat treatable castings.In the present work the New Rheocasting Process is introduced and the influence of heat treatment on mechanical properties of the New Rheocast alloy A356 is discussed.The alloy A356 is cast under ideal New Rheocasting conditions into a step die on an UBE HVSC 350 Squeeze Casting machine. As-east, TS and T6 heat treatment conditions with variations in solutionizing and aging time/temperature parameters are applied and the samples are tested by tensile testing. Alternatively, the same heat treatment conditions are applied to conventional Squeeze Casting parts and compared with New Rheocasting.Questions of potential cost savings due to modified heat treatment conditions are also addressed in this paper."

Jan 1, 2000

By W. Petruk

A study was performed to determine whether mineral textures affect are breakage during grinding, and to establish a correlation between are breakage and mineral liberation. A base metal are from the Brunswick No. 12 deposit in New Brunswick, Canada was ground for different periods of time in a laboratory ball mill, and both the unbroken are and the ground products were studied by image analysis. Similar size distributions were obtained for material from the 15-minute grind in a laboratory ball mill (K. 0 67 pm), for the grinding circuit discharge from a commercial mill (K. 0 = 59-72 pm), and for pyrite grains in unbroken are (K,. = 74 pm). This similarity indicates that the 1S-minute grind separated weakly adhering pyrite grains along grain boundaries, and represents the limit of easy breakage for the are. At this grind (15 minutes) large discrete are mineral grains and weakly adhering interstitial fillings aIrong pyrite were liberated. On the other hand, the 15-minute grind neither separated rooderately bonded pyrite grains nor released rooderate1y bonded interstitial minerals from pyritei a 45-minute grind (K.. 31 pm) in a laboratory ball mill was required. For Brunswick No. 12 are, a 45-minute grind in a laboratory ball mill (Keo = 31 pm) is equivalent to regrinding in a commercial mill (K ?? Fl:$ 30 pm). Grinding beyond 45 minutes in the laboratory ball mill broke the are by fracturing pyrite across grain boundaries and by Chipping grain edges. Such intense grinding (longer than 45 minutes) did not markedly increase sphalerite liberation. In contrast, the intense grinding increased galena liberation because a significant proportion of the galena occurs as minute inclusions in pyrite. These findings show that ore breakage and coincident liberation depend upon size distributions, intergrowths, and mode of occurrence of the minerals in an ore.

Jan 1, 1988

By Jared Ball, Darren Snashall, Paul Telford, Pengfu Tan, Ben Hogg

"The foamed converter charges were up to 3 8 per month in Xstrata Copper Smelter at Mount Isa. The issue of high converter foamover frequency had remained unsolved for many decades in Mount Isa. A thermodynamic model of copper P-S converter and a viscosity model of converter slag have been developed to simulate the slag blow and copper blow, in order to understand the mechanism of converter foamover. The model predicts the chemistry and viscosity of slag during slag blow and copper blow. The effects of oxygen potential, charge of dirty reverts, slag carryover, under-blowing, over-blowing, and temperature on the foamover and viscosity of slag in copper blow have been discussed. A theory has been developed to understand the mechanism of converter foamover. The practical solutions have also been developed and implemented in Mount Isa Copper Smelter. Some improvements of the industrial operations have been presented. After a series of improvements, the number of foamed charges per month in the converter operations has been decreased significantly from 35 in Aug 2008 to only one per month in 2009/2010.1. IntroductionThe Copper Smelter in Mount Isa receives the concentrate containing about 25% copper and produces anode copper that contains about 99% copper. There are several stages in the process. The first stage carries out in the ISASMELT™ furnace. The ISASMELT™ process produces a molten copper matte containing about 60% copper. An iron-silica slag and a sulfur dioxidebearing off-gas are the by-products of the process. The slag is taken to the slag dams for cooling before it is recycled through the Mount Isa Copper Concentrator.The matte is sent to Peirce-Smith converters. The converters further remove iron and sulphur to produce blister copper which contains about 97% copper. The anode furnaces remove any remaining sulphur and oxygen to produce anode copper that is about 99. 7% pure. This is cast into anodes and sent to the Xstrata Copper Refinery in Townsville for final refining.In the copper pyrometallurgical industrials, slag foaming is an important phenomena which occurs when the gas bubbles have stability and not rupture. Foaming greatly increases the interfacial area between matte, slag and gas and is essential for the operation of high intensity smelting processes. However, foaming or foamover is undesirable in P-S converter since it can damage the equipment and injure the operators. Figure 1 shows that the whole process of a foamover development in a converter."

Jan 1, 2011

By Takashi Ikeda, Masafumi Maeda

"Demand for solar cells is increasing linearly throughout the world. Last year production totaled 3000 tons worldwide. The market size of solar silicon is expected to increase further because of international ""political"" demand to reduce carbonaceous emission from energy consumed. Most elemental silicon is produced by the carbon reduction of Silica in an electric arc furnace. Purity of silicon at this stage is 90-99%. Major impurities are Fe, Ti, Ca· and Al, and minor ones are P, B and carbon. The oxidizing metallurgical process is no longer effective to remove transitfon metals because those are less noble to silicon. Nonmetallic impurities such as phosphorus and boron must be reduced to 0.001ppm for semiconductor use. The most common process for high purity silicon is the Siemens C process, which is basically distillation of hydro-chlorinated silicon followed by CVD of SiHCl3. The cost of such silicon is expensive to allow its popular use in solar cells. Currently scrap silicon -of semiconductors is used for this; however, the supply-of that scrap is limited to just a portion of semiconductor production.In this paper world demand for silicon will be reviewed and some of the processes proposed summarized.IntroductionSilicon is element 14 in atomic number and has an atomic weight of 28.0855. Little elemental silicon is found in the earth, and it is mostly found as oxides or silicate. The Clark number of silicon is very large and the second in its number. If we were discussing the volatility of silicon element on the globe, we would never worry about it. However, it is very difficult to obtain pure elemental silicon because a high purity silicon compound is very rare. In most cases these are silica (silicon oxide SiO2). As shown in Table 1, there are many grades of silica ore classified mainly by their content of iron and alumina."

Jan 1, 2000

By P. Tim Johnson

Relentless increases in demand for nickel and vanadium for uses such as steelmaking, catalysts and battery materials, plus the growing financial and environmental costs of their primary extraction, have led to much interest in potential secondary sources of these metals. The presence of such metals in heavy fuel oils, bitumen and related materials offers both opportunities and challenges for potential extraction methods, especially with the growing production and importance of metal-rich fossil fuels around the world. For several decades, Tetronics’ DC plasma smelting technology has been used for the recovery of metals such as nickel and chromium from stainless steel melt dusts and other wastes in compact, environmentally-friendly and efficient plants. This paper explores the suitability of DC plasma smelting as part of a wider flowsheet with feed preparation and aluminothermic reduction techniques for smaller-scale extraction operations based on this important niche secondary source of these key metals.