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The phase relationships of the complex multi-component systems in the liquid-phase oxidization and separation process related with the chromate cleaner production are investigated theoretically and experimentally. The phase diagram of main system Fe-Cr2O4-KOH-O2 of oxidization process and the relationship of its standard Gibbs free energy change with temperature are calculated. A series of phase diagrams of the separation process at different temperatures, such as K(Na)OH-K (Na)2CrO4-H2O, KOH-KAlO2-H2O,K(Na)OH- K(Na)2CO3-H2O, K(Na)OH-K(Na)HCO3-H2O and K(Na)HCO3-K(Na)2CrO4-H2O have also been calculated. Some experiments are carried out to verify the calculated results. Our results showed that the sub-molten salt media are suitable for the oxidization and separation processes; FeCr2O4 can be oxidized across a wide range of temperature; K (Na)2CrO4 can be separated from K(Na) AlO2 system at appropriate temperature and proper concentration; the crystallization of carbonate is easier than that of K(Na)2CrO4.