Pyroelectrometallurgical processing of bismuth-containing oxides

In this work, we substantiate and develop a general pyroelectrometallurgical technology for processing bismuth dross and oxides (the intermediate products of lead bullion refining by the Betterton-Kroll process) to obtain crude bismuth. The research focuses on bismuth dross (3–5% Bi; 80–85% Pb) remelted at 500–600°С in the presence of NaNO3 and NaOH, as well as the obtained alkaline melt (bismuth oxides, 1–5% Bi; 60–70% Pb). The conducted experiments allowed us to determine optimal parameters of the main steps of processing bismuth oxide, as well as the characteristics of obtained products. Reduction smelting of bismuth oxides at 1150°C (with the addition of sodium carbonate, quartz and fine coke in the amount of 66, 25 and 5% of bismuth oxides mass, respectively) is proposed, leading to bismuth lead formation. Its decoppering is carried out at 350–600°C with 2.0% sulfur (by its weight), added to the melt. We propose to carry out the alkaline treatment of the decoppered Pb-Bi alloy at 500oC in contact with sodium hydroxide, sodium nitrate and sodium chloride, taken in amounts up to 10.2, 8.3 and 1.4% by weight of bismuth lead, respectively. Subsequent electrolysis comprises electrolytic processing of purified Pb-Bi alloy ingots at 550oC. The electrolyte consists of a melt with the following composition, %: NaCl – 7, KCl – 35, PbCl2 – 18 and ZnCl2 – 40. As a result, two end products were obtained by the proposed bismuth oxide processing. The anodic product at the second stage of electrolysis, crude bismuth (yielded 1.1% by the weight of oxides) contains 93.62% Bi and 4.14% Pb, extraction from oxides amounts to 19.0% Bi and 0.1% Pb. About 1.2% Bi and 9.1% Pb of their initial content in the oxides are transferred to the cathodic product containing 0.033% Bi and 97.83% Pb (the yield equalled 5.1% of the oxides).

Recycling of bismuth oxides

Introduction. The paper is devoted to the creation of an environmentally safe, technologically efficient and cost-effective high-performance integrated scheme for the recycling of lead-containing industrial products and waste, in particular, bismuth oxides and drosses formed during the melting of copper-electrolyte sludge, with the production of commodity monoelement products. To solve the problem, a combined technology is used, which is based on hydrometallurgical operations that allow separating chemical elements with similar properties with high extraction into finished products. The aim of the work is to study and develop fundamental approaches and rational integrated technologies for recycling bismuth drosses and oxides-industrial products of refining rough lead, using reducing melts of raw materials and bismuth-enriched sludge, electrolysis of bismuth lead to obtain rough bismuth containing ≥ 90 % Bi with its direct extraction of ≥ 70 %. Methods and approaches: melting at a temperature of 1,100…1,150 oC a charge of optimal composition containing bismuth oxides, sodium carbonate, silicon dioxide and carbon. Novelty: a decrease in the content of noble metals and accompanying chalcogenes in secondary copper-containing raw materials with an increase in the amount of impurity elements. Results and discussion: joint melting (1,100…1,150 °C) of bismuth oxides, sodium carbonate, silicon dioxide and carbon, taken in the mass ratio 100 : (15‒66) : (11‒25) : (5‒7), allows to transfer 89.0 – 93.6 % of bismuth and 99.5 ‒ 99.7 % of lead from the initial oxides to bismuth lead containing ~7 % Bi and ~80 % Pb. The main phase of the Pb-Bi alloy is elemental lead. The increased flux consumption leads to an increase in the amount of recycled silicate slags that are poor in target metals, into which it passes,%: 1.4 Bi; 2 Pb; 47 Zn; 23 Sb; 33 Sn. Main slag phases are following: Na2CaSiO4, Na4Mg2Si3O10, MgO, Pb, ZnS, PbS. The practical relevance is determined by the optimal mode of reducing melting of bismuth oxides (100 %) to obtain lead bismuth, %: 66 Na2CO3, 25 SiO2, 5 C; the process temperature is 1,150 ° C. The presence of impurities makes it necessary to introduce reagent treatment of lead bismuth into the technological scheme for recycling bismuth oxides. Decontamination and alkaline softening will make it possible to obtain a Pb-Bi alloy suitable for pyroelectrometallurgical recycling.

Synthesis, structure, and superconductivity of B-site doped perovskite bismuth lead oxide with indium

The synthesis of Ba(Bi0.25Pb0.75)1−xInxO3−δ superconductors provides an example with indium located in the B site with a decreasing Tzeroc due to hole overdoping.