To address the technical challenges involved in the resource utilization of hot metal containing high levels of vanadium (V: 2–5%) and chromium (Cr: 1–5%), this study proposes a novel method based on pyrometallurgical selective oxidation for simultaneously extracting vanadium and retaining chromium. Through thermodynamic analysis and high-temperature smelting experiments, the competitive oxidation behaviors of carbon, vanadium, and chromium were revealed, and the synergistic control mechanism of temperature and oxygen partial pressure was clarified. The results indicate that within a temperature range of 1693–1753 K, adjusted over 1 h, vanadium preferentially oxidizes over carbon and chromium, while carbon effectively suppresses chromium oxidation. By optimizing ω(FeO) (10.0–15.7%), we achieved a vanadium oxidation efficiency (η_V) of 72.5–82.2% and maintained a chromium retention efficiency (100−η_Cr) exceeding 57.1%. Compared to traditional methods, which rely on high-oxygen blowing (oxygen supply: 43–195 kg/tFe), multi-stage roasting, and hydrometallurgical refining, this approach eliminates roasting and hydrometallurgical steps (such as sodium/calcium roasting and the associated leaching–precipitation units), shortens the process chain, reduces oxygen consumption (>80 kg/tFe), and lowers environmental risks (Cr oxidation reduced > 40%). This study establishes a theoretical framework for achieving sustainable V/Cr separation, enhancing resource efficiency and minimizing pollution (e.g., Cr(VI)-containing wastewater, high-salinity NH₄⁺/Na⁺ wastewater).

Ammonium precipitation is widely used to recover vanadium from slag-derived liquors as ammonium metavanadate or polyvanadate, but chromium control is often evaluated less systematically than vanadium recovery. This focused process-diagnostic review draws on the topic-guided literature identified from academic literature sources, preliminary literature-discovery tools, and reference-list tracing. It presents a diagnostic framework integrating V/Cr speciation, cake entrainment, washing response, soluble-ion tracers (Na⁺, SO₄²⁻, Cl⁻), and recycle-accumulation assessment to identify whether product chromium originates from retained mother liquor, solid-associated transfer, or recycle accumulation. The analysis shows that high single-pass vanadium precipitation efficiency alone is insufficient; credible process assessment requires product-Cr source diagnosis, Cr(VI) control, purge/salt-recovery planning, and multi-cycle validation.

To address the technical challenges in the resource utilization of hot metal containing high levels of vanadium (V: 2–5%) and chromium (Cr: 1–5%), this paper proposes a novel method based on pyrometallurgical selective oxidation for the simultaneous extraction of vanadium and retention of chromium. Through thermodynamic analysis and high-temperature smelting experiments, the competitive oxidation behaviors of carbon, vanadium, and chromium were revealed, and the synergistic control mechanism of temperature and oxygen partial pressure was clarified. The results indicate that within the temperature range of 1693–1753 K, vanadium preferentially oxidizes over carbon and chromium, while carbon effectively suppresses chromium oxidation. By optimizing the ω(FeO) (10.0–15.7%), achieving a vanadium oxidation efficiency (ηV) of 72.5–82.2% and maintaining the chromium retention efficiency (1–ηCr) exceeding 57.1%. Compared to traditional methods—which rely on high-oxygen blowing (oxygen supply: 43–195 kg/tFe), multi-stage roasting, and hydrometallurgical refining—this approach eliminates roasting and hydrometallurgical steps, shortens the process chain, reduces oxygen consumption (> 80 kg/tFe), and lowers environmental risks (Cr oxidation reduced > 40%). The study establishes a theoretical framework for sustainable V/Cr separation, enhancing resource efficiency and minimizing pollution.