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By Yoichi Takeda

Copper solubility in SiO2-CaO-FeOx slag equilibrated with copper matte in 10% SO2 atmosphere at 1573K was estimated. Essential parameters are activity coefficients of copper oxide and sulfide, oxygen and sulfur potentials and activity of copper in the slag-matte system. A large number of experiments provide proper parameters to calculate copper solubility in slag, A classical thcrmodynamic model postulating CuO0.5 and CuS0.5 moleculcs assists in estimating copper solubility in slag. Additions of Si02 and CaO reduce copper solubility almost in any condition. Copper loss, that is function copper solubility and slag volume, in the silica saturated SiO2-FeO. binary slag is minimally equilibrated with less than 66% copper matte while copper loss in the 50% FeO.-SiO2-CaO ternary slag saturated with 2CaOSiO2 is minimally equilibrated with over 66% copper matte. This slag composition has potential for continuous copper converting, direct copper production or high-grade matte production.

Jan 1, 2003

By P. Umadevi

In the light of the discovery of the new super-conducting YBa2Cu3O7-x (YBCO), reactions in the Y2O3¬CuO-BaO system at 1300°C was investigated. The search was for any new phase that may be formed in the system at 1300°C (only 950°C reactions are known so far). 35 mixtures of different compositions were prepared and heated at 1300°C. No new phase was obtained. It was found that YBCO is decomposed at this temperature and Y2O3 and BaCO3 are the major components in the solid obtained after firing in air. However, on cooling the melt slowly and annealing at 950°C YBCO reforms. Such reactions on cooling might have implications on processing of the superconductor YBCO for practical applications as well as on its crystal growth by flux method.

Jan 1, 1989

By Lei Zhang, Shining Chen, Lina Wang, Pu Liu, Benquan Fu, Jiannyang Hwang

A three-dimensional (3D) electrode reactor combined with Fenton reagent was used for advanced treatment of coking wastewater from secondary biological treatment. Effects of some key factors on total organic carbon (TOC) removal rate were investigated, and the results were compared with those of the common three-dimensional electrode reactor. Experimental results showed that TOC removal rate could reach 51.7%, when optimal operating conditions were as follows: initial pH value 3.5, H2O2 dosage 17.6mmol/L, reaction time 90min and FeSO4·7H2O dosage 3.5mmol/L. Analytical results from UV absorption spectra indicated that the organic substances in the coking wastewater were well degraded by this system, which provided good experimental basis for the practical application of this process in the treatment of coking wastewater. This can be meaningful for the treatment of other kinds of wastewater.

Jan 1, 2015

By Willem P. C. Duyvesteyn

A novel hydrometallurgical process for Escondida copper concentrates has been developed by The Minerals Laboratory of BHP. The Escondida Process consists of concentrate leaching, solution purification, electrowinning and residue flotation. Part of the copper will be sold as high grade concentrate and part as high purity SX-EW copper. Contrary to previous efforts for the development of a hydrometallurgical process for copper concentrates, this patented process does not advocate the total dissolution of copper. It only aims for the copper that is readily soluble in a mildly oxidizing environment with an ammoniacal or acidic lixiviant. Both lixiviants were studied, but ammonia was preferred because of fast kinetics at ambient temperatures and pressures. By controlling the oxidation potential, the formation of sulfate ions and, consequently, of an ammonium sulfate byproduct, is precluded. These mild leaching conditions also prevent the dissolution of unwanted impurities and result in the production of ultra-high purity electrowon copper. Solution purification is carried out by solvent extraction with LIX-54. The very high loading capacity of this organic results in a compact SX circuit, consisting of two loading, one scrubbing, and one stripping stage. As the organic is selective for simple copper ions, the copper amine complex is broken down and free ammonia is regenerated and recycled for leaching. High purity copper cathodes are produced in a conventional sulfuric acid based electrowinning system. One scrubbing step is needed to separate the ammoniacal circuit from the acid circuit. Limiting copper dissolution to less than 50% also provides an opportunity to produce high grade concentrates by residue flotation. Copper recoveries in excess of 98% with precious metal values reporting to the final concentrate can readily be obtained. Complete breakdown of the copper mineral- pyrite middlings results in a final concentrate grade that can be even higher than the original feed material. The Escondida Process also provides an opportunity to accept lower grade copper concentrates producing improved copper recoveries in the mill and yet high quality concentrates for marketing. The Paul E. Queoeau International

Jan 1, 1993

By Young-Dae Kim, Dong-Sic Kim, Jong-Jin Pak, Kyung-Hyo Do

"Sulfur is one of the most harmful elements in stainless steel (SIS) products and the specification of sulfur content is getting more severe for high grade SIS. In order to accurately control the desulfurization reaction in high chromium containing SIS melts, it is important to know the thermodynamic interaction between chromium and sulfur in Fe-Cr melts over a wide range of chromium content. In this study, the equilibrium sulfur distribution, Ls, between a Ca0-Alz03 slag and Fe-Cr-C,.,-S melts were measured under CO atmosphere in the temperature range of 1823-1923 K. The specific effect of chromium on the activity coefficient of sulfur in the melts was determined with the consideration of carbon effect on sulfur. A separate experiment was carried to determine. Ls between a slag and FeCr- S melts (Cr: 0-30 mass%) at 1873K to check the validity of the thermodynamic parameter determined in the present study.IntroductionFerritic stainless steels containing chromium (Cr) up to 30 mass% have been developed for a good corrosion resistance and a high formability to replace austenitic SIS. Especially, Sulfur (S) causes a reduction of high-temperature strength and the hydrogen induced cracking (HlC) in stainless steel for line pipes. [l]Many studies on the desulfurization of hot metal and liquid steel have been carried out for several decades and they used HzS-H2 gas equilibrium technique for measuring the effects of many alloying elements on the activity coefficient of S in liquid iron. However, the study on desulfurization of Fe-Cr melts was very scarce.[2] In order to accurately control the desulfurization reaction of high Cr stainless steel, it is essential to know the thermodynamic relation between Cr and S in Fe-Cr melt over a wide range of Cr content and temperature.In the present study, the thermodynamic interaction between Cr and S in liquid iron was determined by measuring the equilibrium distribution ratios of S between Fe-Cr-C,.1-S melts containing a wide range of Cr up to 30 mass% and a 55 mass%Ca0-45 mass%Alz03 slag of which the sulfide capacity was pre-determined using Fe-C,a1-S melts in the temperature range of 1823-1923 K. The validity of thermodynamic parameter determined in the present study was checked by measuring the S distribution between a Ca0-Alz03-Mg0 slag of known sulfide capacity and liquid Fe-Cr-S alloy at 1873 K. Using Wagner's formalism, the results of experiment were thermodynamically considered to determine the effect of a specific concentration of Cr on the activity coefficient of S in liquid iron."

Jan 1, 2014

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 I. Goy D. Gaballah

Decontamination of synthetic K2Cr2O 7 solutions containing 10 to 1000 ppm of hexavalent chromium using chemically treated barks have been studied at a laboratory scale. Metal removal from solutions depends on the pH, the initial concentration and the bark species. The use of a pulp density of 2 % in an agitated flask at the optimum pH for 2 hours leads to a percentage chromium removal of about 95 of the initial metallic ions content. Other trials conducted by column percolation permit the determination of the maximum retention capacity of the treated bark. Depending on the bark species, oak or pine, the rate of saturation is 110 and 215 mg of Cr per gram of bark respectively. The incineration of the metal charged barks gives recyclable, ashes containing 36 and 54 % of chromium metal for the oak and pine barks respectively. Experiments, of Cr6+ removal from industrial effluents containing up to 1800 ppm have been carried out on the semi-pilot plant scale. They have lead to the elimination of about 90 % of hexavalent chromium from this industrial waste solution. Further studies are conducted in order to define the hexavalent chromium binding mechanisms on bark constituents.

Jan 1, 1992

By Hidefusa Takahara, Koichi Miyake, Dierk Raabe

"Mechanical properties of copper wires were examined. The copper wires containing 5-10 mass % chromium and 1-3 mass % silver were produced through heavily cold deformation. It was expected that the copper wire was easily fractured during cold deformation because of the existence of brittle chromium phase in the alloy. In fact, the copper wire was fractured due to large work hardening, when the true strain [n] exceeded 5. However, the copper wire annealed at 1273K for 6 ks ·in the middle of deformation process could be smoothly drawn to 11=8. After precipitation treatment for silver phase at 473k for 1.8 ks, the wire was able to further drawn to n=8.4. The final deformed wire showed tensile strength higher than 1200MPa.IntroductionDownsizing of electronic devices has led to the demand of finer and higher strength materials for cables. Conventional copper alloys have about 800MPa in ultimate tensile strength. These strength are mainly obtained by precipitation hardening. Nowadays, a process for higher strength wire has been developed, where dual phase copper alloy is used. When it is drawn heavily, the' second phase is elongated along drawing direction and the wire gets high strength due to fiber reinforcement (1). That alloy is so called in-situ formed fiber reinforced ·alloy. Cu-Ag(2), Cu-Nb(3) and Cu-Cr(4) systems are well known as such alloys. It is also well known that chromium is brittle material except single crystal and high purity of chromium. However, Mihara et al. C5l have achieved 1 GPa in ultimate tensile strength in the Cu-Cr-Zr and Cu-Cr-Ti alloys by appropriate thermo-mechanical processing.In this study, the Cu-Cr-Ag systems were investigated: The alloys contained 10 or 5% chromium and 3 or 1 % silver. It was demonstrated that silver precipitated in copper matrix contributed on further hardening."

Jan 1, 2000

By Yilin Fang, Alain Bonneville, Timothy. D. Scheibe, Zhijie Xu

"We present a hydro-mechanical model for geological sequestration of carbon dioxide. The model considers the poroelastic effects by taking into account the coupling between the geomechanical response and the fluid flow in greater detail. The simplified hydro-mechanical model includes the geomechanical part that relies on the linear elasticity, while the fluid flow is based on the Darcy's law. Two parts were coupled using the standard linear poroelasticity. Analytical solutions for pressure field were obtained for a typical geological sequestration scenario. The model predicts the temporal and spatial variation of pressure field and effects of permeability and elastic modulus of formation on the fluid pressure distribution.IntroductionIn order to achieve a substantial reduction of CO2 emissions and alleviate the atmospheric carbon problem, massive scale carbon sequestration is required involving millions of tons of carbon dioxide injection over several decades. The geomechanical response is important upon the injection of substantial supercritical carbon dioxide into deep geological formations. Supercritical CO2 is less dense than brine waters and the buoyancy driven flow of CO2 requires the aquifer to be capped by low permeability rock (""caprock"") to prevent the upward migration of C02 (as shown in Fig.1 ). Massive scale injection of C02 changes the overall stress state in the caprock and formation. This change leads to large deformation that can damage the caprock, create fractures, and open new flow paths for supercritical C02. Therefore, a coupled hydromechanical model becomes essential for the caprock integrity analysis."

Jan 1, 2012

By Alicia Esther Ares

This study was conducted to investigate the directional solidification of Zn-20%A1 and Zn20% A1-1O%Si-3o/oCu alloys under different conditions of heat transfer at the metal/mould interface. The type of structure obtained in both cases was analyzed and related to the solidification thermal parameters such as cooling rate, growth rate, thermal gradient and recalescence which were determined from the temperature versus time curves. These parameters were correlated with the structure-like length of columnar grains and size of equiaxed grains. The metallographic analyses were done performing quantitative metallography and composition analysis of the different alloying elements along the cast samples by SEM (Scanning Electron Microscopy) and EDXA (Energy Dispersive X-Ray Analysis). Correlations between properties, structures and thermal parameters were found.

Jan 1, 2008

By Huimin Lu, Shi Zhou, Lisha Yang

"The Zeolitic imidazolate frameworks (ZIFs) were successfully synthesized by applying a combination of ionothermal synthesis and microwave energies for rapid synthesis. The synthesis was proceeded under various conditions including different raw materials, reaction temperature as well as microwave irradiation time. Zeolitic imidazolate frameworks (ZIFs), also known as coordination polymers, are new type of porous materials formed by inerratic polyhedral in three-dimensional. They are the ideal crystalline substances for gas separation and storage. The assynthesized samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), thermal gravimetric analysis (TGA) and C02 adsorption test. Results illustrated that the synthesized samples had stable structure, high thermal stability (up to 530 °C) and C02 adsorption capacity (10.2 cm3/g at 0°C under ambient pressure). This novel method also showed great advantage with high energy efficiency, safe synthesis conditions, and rapid crystallization time (60 minutes).IntroductionNowadays, carbon dioxide capture has become imperative due to the global warming caused by the increase of C02 in the atmosphere, especially produced by the concentrated sources such as power plants [1]. Zeolitic imidazolate frameworks (ZIFs), also known as coordination polymers, are ideal crystalline substances for gas separation and storage due to their structure diversity, high thermal and chemical stability [2-5]. They are formed by inerratic polyhedra in threedimensional with large cages and small apertures. Traditionally, ZIFs are synthesized by solvothermal method in a sealed autoclave under autogenous pressure [6-9]. However, in order to generate the products, the solvothermal temperature should not be lower than 100°C according to the sovlothermal mechanism. Moreover, at such a temperature, molecules with a low boiling point (such as water) may generate high pressure in reactor which might cause danger [9]. Thus the synthesis requires the equipment to possess resistance to autogenous pressure and corrosion. Further, conventional solvothermal methods need a long time to prepare products, usually a few days, which is a large energy consumption and inefficiency. So it is interesting to synthesis ZIFs through other ways under mild reaction condition with high energy efficiency."

Jan 1, 2012

By J. Leon-Torres, D. M. Stefanescu, P. A. Curreri, S. Sen

"Experiments were performed under terrestrial gravity (lg) and during parabolic flights (10·2 g) to study the solidification and macrosegregation patterns of Al-Cu alloys. Alloys having 2% and 5% Cu were solidified against a chill at two different cooling rates. Microscopic and Electron Microprobe characterization was used to produce rnicrostructural and macrosegregation maps.In all cases positive segregation occurred next to the chill because of the shrinkage flow, as expected. This positive segregation was higher in the low-g samples, apparently because of the higher heat transfer coefficient.A 2-D computational model was used to explain the experimental results. The continuum formulation was employed to describe the macroscopic transports of mass, energy, and momentum, associated with the solidification phenomena, for a two-phase system. The model considers that liquid flow is driven by thermal and solutal buoyancy, and by solidification shrinkage. The solidification event was divided into two stages. In the first one, the liquid containing freely moving equiaxed grains was described through the relative viscosity concept. In the second stage, when a fixed dendritic network was formed after dendritic coherency, the mushy zone was treated as a porous medium.The macrosegregation maps and the cooling curves obtained during experiments were used for validation of the solidification and segregation model. The model can explain the solidification and macrosegregation patterns and the differences between low- and high-gravity results."

Jan 1, 1999

By Joo Hyun Park, Soo Sang Park

The distribution behavior of Pb between molten copper and FetO-SiO2 (-CaO, Al2O3) slags was investigated at 1473 K (1200 oC) and p(O2)=10-10 atm in view of the reaction mechanism of Pb dissolution into the slag. The distribution ratio of Pb (LPb) decreases with increasing CaO content (~6 mass pct) irrespective of Fe/SiO2 ratio (1.4~1.7). However, the addition of alumina into a slag with Fe/SiO2=1.5 linearly decreases the LPb, whereas a minimum value is observed at about 4 mass pct Al2O3 at Fe/SiO2=1.3. The log LPb continuously decreases with increasing Fe/SiO2 ratio, and the addition of Al2O3 (5 to 15 mass pct) into the silica-saturated iron silicate slag (Fe/SiO2 < 1.0) yields the highest Pb distribution ratio. The log LPb linearly decreases by increasing the log (Fe3+/Fe2+) value. The Pb distribution ratio increases and the excess free energy of PbO decreases with increasing Cu2O content in the slag. However, from the viewpoint of copper loss into the slag, the silica-saturated system containing small amounts of alumina is strongly recommended to stabilize PbO in the slag phase at a low Cu2O content.

Jan 1, 2014

By Courtney Young, Jerome Downey

"The various technologies developed for treating spent potlining (SPL) from primary aluminum smelters have been reviewed on several occasions. The technologies generally involve physical, chemical, and thermal processes, either individually or in combination, with the primary objective of total recycle, waste minimization, or complete disposal. In general, those technologies geared for recycling involve separations and are therefore subject to recovery inefficiencies that are attributed to several factors. However, the inefficiencies could be reduced or possibly eliminated if the pots were designed for recyclability. This concept is applied to SPLASH, a recently developed SPL management technology.IntroductionAluminum is produced by molten salt electrolysis via the Hall-Héroult process. The process is conducted in an electrolytic “pot,” which is comprised of a steel frame first lined with insulating refractory brick, and then conductive graphite blocks, which serves as the carbon cathode [1, 2]. These materials are collectively referred to as “potlining.” Anodes comprised of petroleum coke/pitch are suspended above the pot and extend down into the molten cryolite (Na3AlF6) electrolyte. The electrolyte temperature is maintained at approximately 980 °C by resistance heating as low voltage (4-5 volts) and high current (50,000-300,000 amps) are applied across the two electrodes.High purity alumina is added to the cryolite bath, where it dissolves and becomes amenable to aluminum reduction at the cathode:"

Jan 1, 2008

By Sheng-ping He, Ya-bing Zhang, Qian Wang, Kun-peng Xu

A mass of Al2O3 tends to form during the continuous casting process of high manganese high aluminum steel, and the properties of mould flux and the quality of slab are seriously affected. The dissolution rate of Al2O3 into the CaO–SiO2–MgO–Al2O3–F−−Na2O−Li2O−BaO−B2O3 slag system has been investigated at 1573 K by employing rotating cylinder method. This paper focuses on the effect of Na2O, Li2O, B2O3, F−, Al2O3 contents and (CaO+BaO)/(Al2O3+SiO2) ratio on the dissolution rate. Experimental results show that the dissolution rate increases with increasing Na2O, Li2O, B2O3 contents and decreasing Al2O3 content, among which Li2O has the greatest effect on increasing dissolution rate; the dissolution rate increases with increasing F− content in slag A-1, but decreases with that in slag A-2; the dissolution rate increases with (CaO+BaO)/(Al2O3+SiO2) ratio within the range from 0.91 to 1.31. The dissolution rate of Al2O3 into molten flux is mainly affected by the viscosity of the molten flux and the thermodynamic driving force.

Mar 1, 2018

By Wilhelm Wendt

About five years ago we showed that it is possible to use the spectral in- formation in the light emitted by the off-gas flame of a PS converter for on-line production control. Very recently measurements have been performed using improved optical equipment and data evaluation software, resulting in both improved accuracy and the establishment of new optical process parameters. Using the optical signals the slag heats could be stopped at a predetermined Cu content of the white metal with an accuracy of +0.2% Cu m the range 74-78% Cu. A good correlation was found between the slag composition and optical data, providing a possibility for on-line monitoring of the SiO2 content of the slag. The measurements indicate the possibility of predicting the optimum end-point of the copper-making stage and having real time information on the impurity removal. Factors influencing the optical parameters, such as blowrate, Pb content, temperature etc. will be discussed.

Jan 1, 1993

By Guy Deschênes

Thiourea solutions can be used as leach liquors to treat gold ores or slimes. It is also efficient to elute resins or strip solvents that were loaded in cyanides solutions. The hydrogen pressure reduction is a practical step to recover gold and silver from leach solutions, and strips and eluates without any destruction of thiourea. It is a critical point because these processes have to consider the recycling of the liquors to be irore economical. The effect of temperature, pressure, acidity, compotation of the solution and the nature of catalysts on pressure reduction by hydrogen were investigated. An electranetallurgical study was? carried out to investigate the mechanism. The composition of the products was studied by different analytical methods. The process shows a good selectivity to precipitate gold and silver in a thiourea solution containing iron and copper. Gold and silver concentrations can be decreased to 0.2 ppm and 0.1 ppm at respectively 70 KPa H2 and 28°C. No decomposition of thiourea was evident during the tests. Metals such as nickel powder or platinum activate the reaction and improve the reduction.

Jan 1, 1989

By B. R. Westphal

The Integral Fast Reactor (IFR) concept being developed by Argonne National Laboratory is based on the pyrometallurgical processing of spent nuclear metallic fuel with subsequent fabrication into new reactor fuel by an injection casting process. During fabrication, a dilute scrap stream containing uranium alloy fines and broken quartz (Vycor) molds is produced. Waste characterization of this stream, developed by using present operating data and chemical analysis, was used to evaluate different uranium recovery methods and possible process variations for the return of the recovered metal. Two methods, comminution with size separation and electrostatic separation, have been tested and can successfully recover over 94% of the metal. Recycling the recovered metal to the injection casting process was evaluated for the different economic and process impacts. The physical waste parameters and the important separation process variables are discussed relative to their effects on the viability of recycling the material. A discussion of the criteria that is being used to establish the acceptable operating limits is also presented.

Jan 1, 1992

By George Oprea, Tom Troczynski, Joe A. Rigby, Waiman Lo

The refractory lining of the tuyere line in Peirce Smith converters have usually much shorter life in service than the rest of the lining, above or below it. There are already recognized chemical, thermal and mechanical factors which contribute to the wear of the lining. Our study presents the experimental results on microstructural changes occurring on these tuyere line bricks in a nickelcopper converter. The experimental bricks, after use at the tuyere line, were investigated using SEM/EDS and XRD techniques, to identify the mineralogical changes due to interactions with the nickel-copper matte or fayalite type slag at the process temperatures. The microstructural changes were correlated with physical and mechanical properties of the brick before and after use and a wear mechanism was suggested. Although the matte does not theoretically react with the mineralogical components of the brick, a partial oxidation of the Ni-Cu sulphides was identified using a line analysis by SEM/EDS in the densified layer at the hot face, which allows for mineralogical changes at the matte-refractory interfaces, with a high probability of microcrack formation due to the thermal cycling during use. These microcracks were also identified to open through inter-granular fractures parallel to the hot face, which appeared to be the main cause of lost lining during use. The reactions between the fayalite slag and refractory brick could eventually play a role in chemical dissolution of the brick only in the superficial layer at the hot face, as no slag components were identified deep into the brick.

Jan 1, 2009

By R. Kola

Since more than 15 years the Waelz process at "Berzelius" in Duisburg has proved suitable for reprocessing the zinc and lead containing dust and .sludge which inevitably occur in making steel in EAF-plants. The produced Waelz-oxide is agglomerated in a hot-briquetting plant and charged to an Imperial Smelting Shaft Furnace to recover the valuable elements in form of metallic zinc and lead. In view of the actual importance of the dumping problems of the EAF wastes a description of the "Berzelius" treatment route is given but also the situation in Western Europe is illustrated. Dust from stainless steel production is successfully treated in the Scan Dust Plasma Process in order to recycle Chromium and Nickel, while the resulting Zinc-Dust is treated via the Waelz-ISF-Route. For treatment of low Zinc-containing dust, sludge and fines from integrated steelworks, pilot scale tests have been carried out successfully in the Circulating Fluid Bed in order to recover metalized iron and .zinc/lead fume. A 30,000 tpy Demonstration Plant is planned?.

Jan 1, 1990