Medieval Pb (Cu-Ag) Smelting in the Colline Metallifere District (Tuscany, Italy): Slag Heterogeneity as a Tracer of Ore Provenance and Technological Process

Archaeological investigations of the Colline Metallifere district (Southern Tuscany, Italy) have highlighted several Medieval sites located close to the main Cu-Pb-Fe (Ag) ore occurrences. This study is focused on the investigation of late-medieval slags from Cugnano and Montieri sites using both geochemical and mineralogical methods to understand slag heterogeneities as result of ore differences and technological processes. Matte-rich slags present in both sites (with abundant matte ± speiss and frequent relict phases) represent waste products related to primary sulphide ore smelting to obtain a raw lead bullion. The distribution of slags between the Ca-rich or Fe-rich dominant composition, and the consequent mineralogy, are tracers of the different ore–gangue association that occurred in the two sites. Silver is present only in very small matte-rich slags and ores enclosed within the mortar of the Montieri site; wastes derived from silver-rich mineral charges were probably crushed for the recovery of silver. Matte-poor slags found at Montieri represent a second smelting; raw lead bullion obtained from matte slags (both Fe- and Ca-rich) was probably re-smelted, adding silica and Al2O3-phase-rich fluxes, under more oxidizing conditions to reduce metal impurities. This second step was probably employed for Zn-rich lead ores; this process helped to segregate zinc within slags and improve the quality of the metal.

Processing of Sb-Pb-Sn-Containing Materials

During the processing of lead containing products and polymetallic alloys the recovery of tin and antimony from technology of lead production is carried out by oxidation refining of decopperized lead with rich oxides (Sn, Sb ≥ 20%).Tin oxides are melted in a short-drum furnaces to lead bullion (> 96% Pb) and tin-rich (> 20% Sn) slag. The slag is melted in an ore-smelting furnace to obtain a Sn-Pb alloy of next composition, %: 56.1 Sn, 18.2 Pb, 14.6 Sb, 6.9 As, which is refined by vacuum distillation with production of rough tin (Sn ≥ 90%). The additional profit of rough tin obtainment (∼310 tons/year), compared with sales of tin slag, is about ∼1.3 million $/year. Keywords: lead, tin, antimony, melting, vacuum distillation

Mineralogical and Chemical Characteristics of Slags from the Pyrometallurgical Extraction of Zinc and Lead

The slags derived from the fire refining of lead bullion, differ distinctly in the mineral composition, which results from the fact that these slags are end products of a series of chemical reactions (of both reduction and oxidation). The most common phases included in the refining slags are sulphates and hydrated sulphates (anglesite, gypsum, ktenasite and namuvite), oxides and hydroxides (wustite and goethite), nitrates (gerhardtite) and silicates (kirschsteinite and willemite). The other phases are sulphides and hydrated sulphides (sphalerite and tochilinite), metals (metallic Pb) and glass. Among the mineral components of these slags can be distinguished—primary mineral constituents, phase constituents formed in the ISP process and lead refining, secondary mineral constituents, formed in the landfill. The slags contain, in chemical terms, mainly FeO, CuO and SO3, PbO, in smaller contents SiO2, Al2O3 and CaO, TiO2, MnO, MgO, K2O, P2O5. The mineralogical and chemical composition indicate that slags may be a potential source of metals recovery and pyrometallurgical processing of these wastes seems to be highly rational.

Cleaner Extraction of Lead from Complex Lead-Containing Wastes by Reductive Sulfur-Fixing Smelting with Low SO2 Emission

A novel and cleaner process for lead and silver recycling from multiple lead-containing wastes, e.g., lead ash, lead sludge, lead slag, and ferric sludge, by reductive sulfur-fixing smelting was proposed. In this process, coke and iron-containing wastes were employed as reductive agent and sulfur-fixing agent, respectively. A Na2CO3-Na2SO4 mixture was added as flux. The feasibility of this process was detected from thermodynamic and experimental perspectives. The influence of Fe/SiO2 and CaO/SiO2, composition of the molten salt, coke addition, smelting temperature, and smelting time on direct Pb recovery and sulfur-fixation efficiency were investigated. The optimal process conditions were determined as follows: WCoke = 15% WPb wastes, W Na 2 CO 3 / W Na 2 SO 4 = 0.7/0.3, Fe/SiO2 = 1.10, CaO/SiO2 = 0.30, smelting temperature 1200 °C, and smelting time 2 h, where W represents weight. Under these optimum conditions, 92.4% Pb and 98.8% Ag were directly recovered in crude lead bullion in one step treatment, and total 98.6% sulfur was fixed. The generation and emissions of SO2 can be avoided. The main phases in ferrous matte obtained were FeS, NaFeS2, Fe2Zn3S5, and a little entrained Pb. The slag was a FeO-SiO2-CaO-Na2O quaternary melt.

Studying Kinetics of Arsenic Recovery from Copper Dross by Alkaline Sulfide Leaching

Copper dross are produced by rough decopperizing of blast furnace lead bullion. During liquation separation of copper dross from lead bullion most of arsenic and copper are concentrated in copper dross, arsenic content is approximately 4% As. Currently the processes for arsenic recovery from copper dross are understudied. In this work the focus is given to studying kinetics of the process for recovering arsenic from copper dross by alkaline-sulfide leaching. Alkaline sulfide leaching allows carrying out selective removal of arsenic into solution, keeping at this non-ferrous and precious metals in leaching residue. The studied method of alkaline sulfide leaching of copper dross provides backgrounds for developing technology that would allow processing of copper dross with selective arsenic removal from lead production cycle. By minimizing circulation of this harmful impurity in lead production it is possible to lessen destructive effect of its aggressive compounds on smelting-units refractory. Kinetics of alkaline sulfide leaching of copper dross was understudied up to date. This work is an attempt to fill the gap.

A process engineering approach to remedy an environmental problem of fugitive lead emissions during lead refining

The refining of lead blast furnace bullion involves the transfer and handling of hot impure lead bullion. Fugitive emissions of lead-containing fumes create a plant hygiene problem. The cause of the emissions is the high vapor pressure of lead and its compounds when lead blast furnace bullion is transferred in an open ladle at ∼1000 °C from the blast furnace and poured into the drossing kettle, and later during the manual skimming of powdery dross. A laboratory study was conducted on a new concept for lead refining that eliminates contact between hot lead and the cnvironment, and thus abates fugitive lead emissions. The new process takes place in two steps: controlled solidification of bullion as it flows from the blast furnace, followed by remelting in a closed centrifuge to separate lead and dross. Refined lead was produced with <0.05% copper and <0.01% of all other impurities. Suggestions are outlined for implementing the process.