The titanium resources in Panxi reign, China, have a high-impurities content of Ca and Mg, which is usually processed by the molten salt chlorination process. This process allows higher Ca and Mg content in its furnace burdens. However, there is a huge amount of molten salt chlorinated slag produced by this process, consisting of complex compounds and waste NaCl/KCl salts. These slags are always stockpiled without efficient utilization, causing serious environmental pollutions. To recycle the NaCl in the slag back to the molten salt chlorination process, a novel process to deal with those molten salt chlorinated slags with phase conversion at high temperature is presented in this paper. The calcium-containing solid phase was generated when Na2SiO3 was added to the molten salt chlorinated slags at high temperature, while NaCl was kept as a liquid. Thus, liquid NaCl was easily separated from the calcium-containing solid phase, and it could be reused in the molten salt chlorination process. The conversion of calcium-containing phases and their separation of NaCl are the key parts of this work, and they have been systematically studied in this paper; thermodynamic analysis, phase transformation behavior, and calcium removal behavior have all been investigated. The calcium removal rate is 78.69% when the molar ratio of CaCl2:Na2SiO3 is 1:1.5 at 1173 K and N2 atmosphere.

The molten salt chlorination method is more suitable to produce TiCl4 using titanium-containing materials with high contents of CaO and MgO in China. However, there is a large amount of molten salt chloride slags generated from the molten salt chlorination process, which contains a variety of chlorides and is difficult to treat, often causing serious environmental problems such as direct piling or landfilling. A novel process was proposed to deal with molten salt chloride slags, and calcium chloride could be effectively removed by this process (as in our previous study). However, magnesium chloride is another impurity which can deteriorate the density and viscosity of the molten salt; it is often found in higher contents, and should be also removed from molten salt chloride slags to efficiently recycle NaCl in novel processes. Na2SiO3 is added to the molten salt chloride slags in the molten state to produce the Mg-containing solid phase, which could be separated with the molten NaCl in novel processes. Thus, the transition of Mg-containing phases and the recovery of NaCl in molten salt chloride slags at high temperature in a novel process were systematically investigated in this work, including thermodynamic analysis, the phase transition behavior of Mg-containing phases, NaCl recovery, etc. The removal rate of Mg was 99.56% when the molar ratio of MgCl2:Na2SiO3 was 1:1.5 at 1273 K and in a N2 atmosphere. The recovery rate of NaCl from the molten salt chlorination slag was 97.62% and the purity of NaCl obtained was 99.35 wt%, which could be used in the molten salt chlorination process.

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