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摘要: 目前鎢冶煉的堿分解工藝，存在用水量大、廢水量大、加工成本高等問題，使鎢冶煉企業面臨著經濟與環保的雙重壓力，不能繼續滿足行業發展需求。對此，在大量白鎢焙燒分解工藝研究的基礎上，提出了酸法焙燒思路，開發出了硫酸鹽焙燒分解白鎢工藝，一步轉型生成WO3。由于白鎢礦焙燒產物的主要雜質為Na2SO4與難溶CaSO4，可采用鹽酸浸出方式進行鎢鈣分離，本文采用等溫平衡法，考察對比了WO3、CaSO4與WO3–CaSO4在HCl–Na2SO4溶液中的溶解行為，結果表明：WO3與CaSO4在鹽酸中的溶解度相差較大，CaSO4在鹽酸中溶解度隨溫度、鹽酸濃度的升高而增大，在溫度80 ℃、鹽酸濃度3 mol·L–1的條件下，硫酸鈣在鹽酸中的溶解度達到峰值55 g·L–1，而Na2SO4可顯著降低CaSO4在鹽酸中的溶解度，縮小CaSO4與WO3在鹽酸中的溶解差，WO3溶解度則維持在0.3～3 g·L–1范圍內，結合目前成熟的低鎢回收工藝，能將該部分溶解鎢有效地回收，即控制一定的溶解條件有利于鎢鈣高效分離。Abstract: There are numerous issues in the mainstream process of alkali decomposition of tungsten ores, such as large water consumption, large amounts of wastewater, and high processing costs, which add the dual pressure of economic and environmental protection on smelting enterprises and prevent them from meeting the industry’s development needs. As a result of a series of studies on scheelite roasting and decomposition processes, our team innovatively proposed the use of acid roasting to develop the process of sulfate decomposition of scheelite so that CaWO4 in the scheelite could be transformed directly into WO3. In addition to WO3, the roasting products contained soluble Na2SO4 and insoluble CaSO4. Because CaSO4 can be dissolved in hydrochloric acid, it can be separated from WO3 via hydrochloric acid leaching to further enrich WO3, resulting in a higher-grade material for subsequent procedures. In the presence of Na2SO4, its effect on the dissolution of WO3 or CaSO4 in hydrochloric acid will directly determine the separation effect of calcium and tungsten in the roasting products. Thus, using pure substances such as WO3, CaSO4, and Na2SO4 as raw materials, the dissolution behaviors of WO3, CaSO4, and WO3–CaSO4 in HCl–Na2SO4 solution were investigated separately via isothermal equilibrium dissolution to investigate the effects of hydrochloric acid concentration, sodium sulfate concentration, dissolution time, and dissolution temperature on the solubility of WO3, CaSO4, and WO3–CasO4 in HCl–Na2SO4 solution. The analysis shows that WO3 and CaSO4 have very different solubilities in hydrochloric acid. The solubility of CaSO4 in hydrochloric acid increases with temperature and hydrochloric acid concentration when the dissolution time is 0.5–2.5 h, the hydrochloric acid concentration is 1–5 mol·L?1, the molar ratio of HCl and Na2SO4 is 1∶2–2∶1, and the dissolution temperature is 40–80 ℃. The solubility of calcium sulfate in hydrochloric acid increases with the increase in temperature and hydrochloric acid concentration. When the temperature is 80 ℃ and the concentration of hydrochloric acid is 3 mol·L?1, the solubility of calcium sulfate in hydrochloric acid reaches a peak of 55 g·L?1. Due to the same ion effect, Na2SO4 can significantly reduce the solubility of CaSO4 and narrow the solubility difference between CaSO4 and WO3 in hydrochloric acid. CaSO4 has the highest solubility in HCl–Na2SO4 solution at 17.04 g·L?1. The dissolved WO3, whose solubility is maintained at 0.3–3 g·L?1, can be effectively recovered by using the current mature low-tungsten recovery process. Therefore, when CaSO4 and WO3 coexist in hydrochloric acid, increasing the concentration of hydrochloric acid and the dissolution temperature while decreasing the concentration of Na2SO4 can increase the solubility difference between them and achieve separation.
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Key words:
- calcium sulfate /
- tungsten trioxide /
- sodium sulfate /
- hydrochloric acid /
- solubility
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圖 1 鹽酸濃度、溫度對CaSO4在鹽酸中溶解的影響
Figure 1. Influence of hydrochloric acid concentration and temperature on the solubility of CaSO4 in hydrochloric acid
圖 3 時間對WO3在鹽酸中溶解的影響
Figure 3. Influence of time on the solubility of WO3 in hydrochloric acid
圖 4 溫度對WO3在鹽酸中溶解度的影響
Figure 4. Influence of temperature on the solubility of WO3 in hydrochloric acid
圖 5 鹽酸濃度對WO3在鹽酸中溶解度的影響
Figure 5. Influence of hydrochloric acid concentration on the solubility of WO3 in hydrochloric acid
圖 6 n(HCl):n(Na2SO4)對WO3在鹽酸中溶解度的影響
Figure 6. Influence of n(HCl):n(Na2SO4) on the solubility of WO3 in hydrochloric acid
圖 7 WO3–CaSO4在鹽酸溶液中的溶解情況
Figure 7. Dissolution of WO3–CaSO4 in HCl–Na2SO4 acid solution
圖 8 WO3–CaSO4在HCl–Na2SO4溶液中的溶解情況
Figure 8. Dissolution of WO3–CaSO4 in HCl–Na2SO4 solution
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