Iron sulfate, in particular FeSO4·7H2O, is derived from titanium dioxide production and the steel pickling process. Regarding TiO2 manufacturing, the amount of the resultant FeSO4·7H2O can be as high as 6 tons per ton of produced TiO2, leading to a huge amount of ferrous sulfate heptahydrate, which is considered an environmental and economic concern for the titanium dioxide industry in European countries. The present paper focuses on the thermal treatment of ferrous sulfate (heptahydrate and monohydrate) samples under different conditions. Nonisothermal thermogravimetric (TG) analysis was used to study the behavior of iron sulfate samples at temperatures of up to 1000 °C in Cl2 + O2, O2, and N2 atmospheres. Results showed that the dehydration of iron sulfate heptahydrate in nitrogen started at room temperature and resulted in iron sulfate tetrahydrate (FeSO4·4H2O). The ferrous sulfate monohydrate (FeSO4·H2O) was formed at temperatures close to 150 °C, while the anhydrous ferrous sulfate (FeSO4) was obtained when the samples were heated in nitrogen at over 225 °C. The kinetic features of FeSO4 decomposition into Fe2O3 were revealed under isothermal conditions at temperatures ranging from 500 to 575 °C. The decomposition of iron sulfate was characterized by an apparent activation energy of around 250 kJ/mol, indicating a significant temperature effect on the decomposition process. The obtained powder iron oxide could be directed to the agglomeration unit of iron and the steelmaking process.

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The investigation presented here features the design of a cleaner and greener chemical process for the conversion of industrial wastes into super-oxidizing materials. The waste of interest is the iron sulfate heptahydrate (FeSO4·7H2O) mainly generated through the sulfate route used for titanium dioxide industrial production. The products of this transformation process are alkali ferrates (A2FeO4, A = Na, K) containing iron in its hexavalent state and considered as powerful oxidants characterized by properties useful for cleaning waters, wastewaters, and industrial effluents. The proposed process includes two steps: (i) The first step consisting of the pre-mixing of two solids (AOH with FeSO4·xH2O) in a rotary reactor allowing the coating of iron sulfate in the alkali hydroxides through solid–solid reactions; and (ii) the second step involves the synthesis of alkali ferrates in a fluidized bed by oxidation of the single solid obtained in the first step in diluted chlorine. The chemical synthesis of alkali ferrates can be carried out within a timeframe of a few minutes. The usage of a fluidized bed enhanced the energy and mass transfer allowing a quasi-complete control of the ferrate synthesis process. The alkali ferrate synthesis process described here possesses many characteristics aligned with the principles of the “green chemistry”.