Abstract Industrial side streams, such as steel slag, can contain significant amounts of vanadium (V), and its recovery is important for their beneficial use. This study presents a simple approach for recovery of NH4VO3 by direct crystallization from (NH4)2CO3 matrix without significant reagent additions and a V separation stage. This study investigated several factors (seed crystals, ultrasonic pretreatment, pH, vanadium concentration [V], Fe and Mn impurities) affecting direct NH4VO3 crystallization from dilute V-containing ([V] 1.2–2.4 g/L) synthetic solutions. Besides [V], pH had a significant effect on crystallization, especially in the presence of a main impurity Fe. Fe precipitated rapidly with an amorphous structure during pH adjustment. At sufficiently low pH (< 6.8), NH4VO3 crystallized slowly after Fe-containing precipitate formation. The total V recovery (R%) reached 81% but due to co-precipitation of V and Fe, V losses (2–35%) varied depending on the variation in Fe concentration. To minimize V loss, washing the Fe-containing precipitate with an alkaline solution was carried out with promising results (V R% 16–80%). The presence of Mn increased V R% despite almost complete co-precipitation with NH4VO3. The utilization of seed crystals accelerated the crystallization, but the effect of a three-minute ultrasonic pretreatment had an insignificant effect. The method was applied to authentic leachates ([V] 1.6 g/L) which showed comparable results (V R% 81%). Based on SEM-EDS, NH4VO3 crystals contained only marginally Si. This study demonstrates the significant applicability of direct NH4VO3 crystallization for dilute V solutions and offers a functional method from an industrial perspective.
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