通过计算反应Gibbs自由能和平衡溶解度对铬酸钠碱性液添加石灰除钒过程进行理论分析,结合红外光谱研究了含钒溶液的结构变化,研究添加石灰除钒时各因素的影响规律.结果表明:在298～373 K的范围内,体系中各离子与氧化钙生成相应钙盐的反应自由能绝对值由大到小的顺序为VO3-、CO32-、SO42-、VO43-、CrO42-;同时,各钙盐间可能存在相互转化,溶液中CO32-能分解CaCrO4和Ca3(VO4)2等钙盐,VO43-能分解CaCrO4.除钒过程中除生成Ca3(VO4)2和Ca2V2O7外,还能生成CaCO3、CaCrO4、CaSO4·nH2O等化合物,这是由于石灰加入量过多所致.溶液结构分析结果表明:随着pH值从13降到9左右,钒酸根由VO43-转化成VO43-和V2O74-共存的结构.除钒实验结果表明:提高溶液pH值、增大n(CaO )/n(V2O5)或加入高活性石灰乳均可提高除钒率,而溶液中CO32-的存在明显降低除钒率；加入理论用量3倍的石灰,溶液pH值降全10左右时,除钒率可达到85％,相对于工业除钒过程钒渣量减少88％左右.
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