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4. Results and discussion 4.1. Thermodynamic equilibrium calculations Gibbs free energy calculations of the extraction reactions (Eqs. (4) and (6)) using HSC 5.1 showed that the extraction of Ca+2-ions from CaSiO3 is thermodynamically possible at temperatures lower than 156 1C, while the extraction of Mg+2-ions from MgSiO3 proceeds at temperatures lower than 123 1C (Fig. 3). Gibbs free energy calculations of the carbonation reactions (Eqs. (5) and (7)) showed that the carbonation of Ca+2-ions proceeds already at temperatures over 45 1C, while the carbonation of Mg+2-ions should only be possible at temperatures over 144 1C. The calculations also show that the extraction reactions are exothermic (DHo0), while the carbonation reactions are endothermic (DH40). The net reactions of calcium silicate carbonation (Eqs. (4) and (5)) and magnesium silicate carbonation (Eqs. (6) and (7)) are both exothermic. The dissolution of the various species of blast furnace slag in acetic acid was studied in more detail by calculating the chemical composition at thermodynamic equilibrium using HSC. The input parameters were set to simulate the extraction experiments carried out later on, using 4.2 g of blast furnace slag in a 250 ml aqueous solution of acetic acid (33.3 wt% CH3COOH, 66.7wt% H2O). Only the six largest species in blast furnace slag were used as input data,to simplify the results. All the compounds in the database of HSC 5.1 were used as potential products, except for C,CxHy, and all carbonates, which are unlikely products from the extraction process performed in absence of CO2. The results and input data are summarized in Table 1. The results show that all compounds (except for Ti) are expected to be dissolved in the solution. A large part of the metals dissolved are expected to form acetates, such as magnesium acetate, calcium acetate, and iron(II) acetate.Although Fe, S and Ti are in oxide states in slags, having the input of these in elemental form does not notably affect the outcome of the calculation, since HSC merely calculates the equilibrium composition. Although all compounds are not likely to be formed due to slow kinetics, the modeling results give a hint upon the feasibility of the extraction. |
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