CaO-Al
2O
3-SiO
2=50-42-8% by weight (wt%) eutectic slags, similar in composition to a secondary steelmaking slag, containing 1-15 wt% CaCl
2 were heated to 1798 K. DTA was performed and the system was cooled. Samples were characterized by electron microprobe and X-ray powder diffraction. Four main crystalline phases were present, CaO·Al
2O
3, 2CaO·Al
2O
3·SiO
2, β-2CaO·SiO
2 and 11CaO·7Al
2O
3·CaCl
2. The chlorine phase was very similar to the mayenite phase (12CaO·7Al
2O
3). It formed first at 1321 (±27) K and remained solid as a separate phase because of its high melting point. The rest of the system, upon cooling, crystallized according to the well-known CaO-Al
2O
3-SiO
2 phase diagram. It was seen that if chlorine is present in sufficient amounts (greater than 4.9 wt%), the chlorine phase constitutes 92 wt% of the final slag. Also when the chlorine phase was less than 92 wt% in the final slag, the recovery of chlorine exceeded 90%. For comparison, CaO-Al
2O
3-SiO
2=48-12-40 wt% representing an ironmaking slag, was mixed with 10.0 wt% CaCl
2 and also similarly heated and characterized after cooling. The phases observed were 2CaO·Al
2O
3·SiO
2 and two new chlorine phases, all of which were glassy.
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