Deep-sea mud rich in rare earth yttrium has received lots of attention from the international community as a new resource for Y. A novel process, which mainly includes acid leaching, solvent extraction, and oxalic aci...Deep-sea mud rich in rare earth yttrium has received lots of attention from the international community as a new resource for Y. A novel process, which mainly includes acid leaching, solvent extraction, and oxalic acid precipitation-roasting, is proposed for recovery of Y from deep-sea mud. A series of experiments were conducted to inspect the impacts of various factors during the process and the optimum conditions were determined. The results show that the Y of deep-sea mud totally exists in apatite minerals which can be decomposed by hydrochloric acid and sulfuric acid solution. The highest leaching efficiency of Y is 94.53% using hydrochloric acid and 84.38% using sulfuric acid under the conditions of H^＋concentration 2.0 mol/L, leaching time 60 min, liquid-solid ratio 4：1 and room temperature 25 ℃（only in case of sulfuric acid, when using hydrochloric acid, the leaching temperature should be 60 ℃）. Because of the much lower leaching temperature, sulfuric acid leaching is preferred. The counter current extraction and stripping tests were simulated by a cascade centrifugal extraction tank device. Using 10 vol% P204,15 vol% TBP and 75 vol% sulfonated kerosene as extractant, 98.79% Y^3＋ and 42.60% Fe^3＋ are extracted from sulfuric acid leaching liquor（adjusted to pH = 2.0） after seven-stage counter current extraction with O/A ratio of 1：1 at room temperature, while other metals ions such as Al^3＋, Ca^2＋, Mg^2＋and Mn^2＋ are almost not extracted. The Y^3＋ in loaded organic can be selectively stripped using 50 g/L sulfuric acid solution and the stripping efficiency reaches 99.86% after seven-stage counter current stripping with O/A ratio of 10：1 at room temperature, while only 2.26% co-extracted Fe^3＋ is stripped. The Y^3＋ of loaded strip liquor can be precipitated by oxalic acid to further separate Y^3＋ and Fe^3＋. The precipitation efficiency of Y^3＋ in loaded strip liquor can be 98.56% while Fe^3＋ is not precipitated under the conditions of oxalic acid solution concentration 200 g/L, quality ratio of oxalic acid to Y of 2, and precipitation time 0.5 h. And the precipitate was roasted at 850 ℃ for 3 h to obtain the oxide of Y in which the purity of Y_2 O_3/REO is 79.02% and the contents of major non-rare earth impurities are less than 0.21%.Over the whole process included acid leaching, solvent extraction, and oxalic acid precipitation-roasting,the yttrium yield is 82.04%.展开更多
基金Project supported by Science and Technology Planning Project of Guangdong Province(20168070701022,20168090931003,20168020240004,2017B090907026)National Natural Science Foundation of China(51704081)+1 种基金Ocean Investigation and Research Project of China Geological Survey(GZH201100303-05)Science and Technology Program of Guangzhou(201504010010,201607020022)
文摘Deep-sea mud rich in rare earth yttrium has received lots of attention from the international community as a new resource for Y. A novel process, which mainly includes acid leaching, solvent extraction, and oxalic acid precipitation-roasting, is proposed for recovery of Y from deep-sea mud. A series of experiments were conducted to inspect the impacts of various factors during the process and the optimum conditions were determined. The results show that the Y of deep-sea mud totally exists in apatite minerals which can be decomposed by hydrochloric acid and sulfuric acid solution. The highest leaching efficiency of Y is 94.53% using hydrochloric acid and 84.38% using sulfuric acid under the conditions of H^＋concentration 2.0 mol/L, leaching time 60 min, liquid-solid ratio 4：1 and room temperature 25 ℃（only in case of sulfuric acid, when using hydrochloric acid, the leaching temperature should be 60 ℃）. Because of the much lower leaching temperature, sulfuric acid leaching is preferred. The counter current extraction and stripping tests were simulated by a cascade centrifugal extraction tank device. Using 10 vol% P204,15 vol% TBP and 75 vol% sulfonated kerosene as extractant, 98.79% Y^3＋ and 42.60% Fe^3＋ are extracted from sulfuric acid leaching liquor（adjusted to pH = 2.0） after seven-stage counter current extraction with O/A ratio of 1：1 at room temperature, while other metals ions such as Al^3＋, Ca^2＋, Mg^2＋and Mn^2＋ are almost not extracted. The Y^3＋ in loaded organic can be selectively stripped using 50 g/L sulfuric acid solution and the stripping efficiency reaches 99.86% after seven-stage counter current stripping with O/A ratio of 10：1 at room temperature, while only 2.26% co-extracted Fe^3＋ is stripped. The Y^3＋ of loaded strip liquor can be precipitated by oxalic acid to further separate Y^3＋ and Fe^3＋. The precipitation efficiency of Y^3＋ in loaded strip liquor can be 98.56% while Fe^3＋ is not precipitated under the conditions of oxalic acid solution concentration 200 g/L, quality ratio of oxalic acid to Y of 2, and precipitation time 0.5 h. And the precipitate was roasted at 850 ℃ for 3 h to obtain the oxide of Y in which the purity of Y_2 O_3/REO is 79.02% and the contents of major non-rare earth impurities are less than 0.21%.Over the whole process included acid leaching, solvent extraction, and oxalic acid precipitation-roasting,the yttrium yield is 82.04%.
