Vanadium containing sludge is a by-product of vanadium pentoxide obtained by hydrometallurgical methods from vanadium slag that can be estimated as a promising technogeneous raw material for vanadium production. The phase analysis of vanadium-containing sludge by the X-ray diffraction method showed that it contains vanadium in spinel form (FeO∙V₂O₃). The various oxidation roasting methods for sludge treatment were studied for increasing vanadium extraction into the solution. It showed that the most effective additive is 1% CaCO₃ at a roasting temperature of 1000 °C. Oxidation roasting of vanadium-containing sludge with the additive led to an increase in the acid-soluble form of V₂O₅ from 1.5% to 3.7% and a decrease in the content of FeO∙V₂O₃ from 3% to 0.4%. These results confirm the efficiency of the application of oxidation roasting to convert vanadium compounds into acid-soluble forms. The conversion mechanism of spinel to acid-soluble phases during oxidation roasting with additives was investigated by thermogravimetric analysis and thermodynamic simulation. It showed that the formation of acid-soluble calcium vanadates during oxidation roasting without additives occurs at temperatures above 800 °C while CaCO₃ addition allows one to reduce this temperature to 600 °C.

A big amount of solid wastes or dump sludges is generated after leaching vanadium (V) from a roasted mixture. As the vanadium content in these tailings is comparable to its concentration in traditional vanadium sources such as titanomagnetite ores or a vanadium converter slag, these wastes could be recycled to extract additional vanadium. Therefore, this research was aimed on studies of vanadium-containing sludges resulting from hydrometallurgical production of vanadium pentoxide to find an optimal technology for V extraction. The material composition of industrial and synthetic sludge samples was studied by X-ray fluorescence analysis (XRF), X-ray diffraction (XRD), secondary ions mass spectroscopy (SIMS), and X-ray photoelectron spectroscopy (XPS, ESCA). The paper demonstrates the presence of vanadium in sludges, not only in spinels in 3+ oxidation degree, but also in other compounds containing V⁴⁺ and V⁵⁺. It was found that vanadium substitutes a set of elements in minerals except spinel. The dependence between the content of insoluble vanadium compounds and V oxidation degree was determined.

The paper describes hydrometallurgical methods to recycle wastes of vanadium pentoxide chemical fabrication. Sludges containing a significant amount of V₂O₅ can be considered as an additional source of raw materials for vanadium production. We studied the one-stage leaching method using various iron-based reductants for converting V⁵⁺ to V⁴⁺ in a solution allowing to precipitate V when its concentration in the solution is low. As a result of the reduction leaching with further precipitation, we obtained concentrates with V₂O₅ content of 22–26% and a high amount of harmful impurities. Multistage counterflow leaching can be used to fabricate solutions with vanadium pentoxide concentration suitable for vanadium precipitation by hydrolysis and adding ammonium salts. The solutions with V₂O₅ content of ≈15 g/L can be obtained from the initial sludge by three-stage counterflow vanadium leaching. A concentrate with a content of 78 wt% V₂O₅ can be precipitated from these solutions at pH = 2.4 by adding ammonium chloride. Additionally, concentrate with V₂O₅ content of ≈94 wt% was precipitated from the solution with a concentration of >20 g/L V₂O₅ obtained from the roasted sludge. The concentrates were purified for increasing the vanadium content to 5–7%. The consumption and technological parameters of the considered processes are presented in the paper.

Metallurgical vanadium-containing converter slag could be used as an alternative vanadium source. The development of a physico-chemical basis for the comprehensive processing of industrial vanadium-containing debris requires information about their elemental composition as well as the oxidation degrees of the elements and forms of compounds in order to solve two key problems: a better utilization of industrial wastes and a lowering of environment impact. This research was aimed at the development of methods to determine the fractions of elements and their oxidation degrees in vanadium-containing industrial debris exemplified by basic oxygen converter vanadium slags. A set of bulk and surface analysis methods (X-ray fluorescence analysis (XRF), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS)) was used for this purpose: based on results of elemental analysis, SEM detects the oxide phases of metals, while an analysis of the XPS lines’ fine structures provides fractions of corresponding elements with definite oxidation degrees. In this way, one can determine the fractions of vanadium in multiple oxidation degrees in slags and can properly select the chemicals and parameters of chemical processes for its fullest extraction.

The results of the processing of ash from the combustion of fuel oil after roasting with the addition of Na₂CO₃ followed by aluminothermic melting are presented. As a result, metallic nickel and vanadium slag were obtained. Studies of slag, metal, and deposits on the electrode were carried out. The resulting metal contains about 90 wt% Ni. The main phases of scurf on the electrode are a solid solution based on periclase (Mg_{1–x–y–z}Ni_xFe_yV_zO), sodium-magnesium vanadate (NaMg₄(VO₄)₃), and substituted forsterite (Mg_2–x–yFe_xNi_ySiO₄). The processing of ash made it possible to significantly increase the concentration of vanadium and convert it into more soluble compounds. Vanadium amount increased from 16.2 in ash to 41.4–48.1 V₂O₅ wt% in slag. The solubility of vanadium was studied during aqueous leaching and in solutions of H₂SO₄ and Na₂CO₃. The highest solubility of vanadium was seen in H₂SO₄ solutions. The degree of extraction of vanadium into the solution during sulfuric acid leaching of ash was 18.9%. In slag, this figure increased to 72.3–96.2%. In the ash sample, vanadium was found in the form of V⁵⁺, V⁴⁺ compounds, vanadium oxides VO₂ (V⁴⁺), V₂O₅ (V⁵⁺), and V₆O₁₃, and nickel orthovanadate Ni₃(VO₄)₂ (V⁵⁺) was found in it. In the slag sample, vanadium was in the form of compounds V⁵⁺, V⁴⁺, V³⁺, and V^(0÷3)+; V⁵⁺ was presented in the form of compounds vanadate NaMg₄(VO₄)₃, NaVO₃, and Ca_xMg_yNa_z(VO₄)₆; V³⁺ was present in spinel (FeV₂O₄) and substituted karelianite (V_{2–x–y–z}Fe_xAl_yCr_zO₃). In the obtained slag samples, soluble forms of vanadium are due to the presence of sodium metavanadate (NaVO₃), a phase with the structure of granate Ca_xMg_yNa_z(VO₄)₆ and (possibly) substituted karelianite (V_{2–x–y–z}Fe_xAl_yCr_zO₃). In addition, spinel phases of the MgAl₂O₄ type beta-alumina (NaAl₁₁O₁₇), nepheline (Na_4–xK_xAl₄Si₄O₁₆), and lepidocrocite (FeOOH) were found in the slag samples.