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This invention relates to a protective slag for sulfur-containing free-cutting steel crystallizers using photovoltaic silicon mud and its preparation method. The protective slag of this invention contains, by mass percentage, 30.6–31.6 wt% CaO, 36.7–37.7 wt% SiO2, 6.1–7.1 wt% Al2O3, 8.2–9.2 wt% Na2O, 5.0–6.0 wt% F, and 9.0–10.0 wt% C. 固 H2O up to 0.5 wt%; C 固 The carbon in the protective slag is fixed. Raw materials include 7-9 wt% silica mud, 14-16 wt% blast furnace slag, 24-26 wt% phosphorus slag, 14-16 wt% silicate cement, 4-6 wt% wollastonite, 10-12 wt% soda ash, 2-4 wt% fluorite, 6-8 wt% cryolite, and 10-12 wt% carbon powder. The preparation method includes batching, slurry preparation (solid content 40-45%), spray granulation (spray gun orifice diameter 1.0-1.5 mm, inlet temperature 450-480℃), and post-treatment. This invention enables the utilization of photovoltaic silica mud, reducing the cost of protective slag containing silica mud by 870 yuan per ton, and increasing the flaw detection pass rate of continuously cast billets from 25.99% to 55.17%, thus possessing both energy-saving and emission-reduction value and a circular economy value.