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    • 1. 发明授权
    • Recovery of fluorine from pond water of wet process phosphoric acid
plants and recycling of defluorinated water
    • 从湿法磷酸厂池塘水中回收氟,脱氟水再循环
    • US4374810A
    • 1983-02-22
    • US45116
    • 1979-06-04
    • Padraic S. O'Neill
    • Padraic S. O'Neill
    • C01F11/22C02F1/52C02F1/58
    • C02F1/5236C01F11/22C02F1/583Y10S210/906Y10S210/915
    • A process for obtaining calcium fluoride from the pond water of phosphoric acid plants and recycling the high phosphate defluorinated water to the pond is disclosed. Sufficient calcium carbonate is added to a solution having a pH of about 0.8, containing about 1% fluoride, 1% phosphate and less than 0.4% sulfate, to raise the pH thereof to 2-3, whereby calcium fluoride is precipitated as a major component, calcium phosphates and calcium sulfates are precipitated as minor components. The calcium fluoride precipitate obtained is washed with raw pond water to reduce the phosphate content and with ammonium carbonate solution to reduce the sulfate content. In this manner an industrially useful fluorspar is obtained. The low fluoride supernatant liquid is then mixed with sufficient raw pond water to bring the pH into the range 1.5-2.0 and the resulting suspension is then held in a lagoon for 5-21 days to permit separation of silica. After separation by sedimentation, the water containing unprecipitated phosphate is returned to the pond for further use. The silica-rich sediment may be further dewatered by centrifugation and used in the phosphoric acid plant to promote better recovery of fluoride. To minimize sulfate contamination of the calcium fluoride product, a separate pretreatment step may be provided to reduce the sulfate content of the pond water to approximately 0.4%. In this step, sufficient calcium carbonate is added to raise the pH of the pond water to about 2.0, and after adequate aging to cause precipitation of calcium sulfate with minimal precipitation of calcium fluoride which precipitates at a higher pH. After pretreatment, the suspension is treated by the first step of the process to remove calcium fluoride.
    • 公开了一种从磷酸植物的池塘水中获得氟化钙并将高磷酸盐脱氟水再循环到池塘的方法。 将足够的碳酸钙加入pH约为0.8的溶液中,含有约1%的氟化物,1%的磷酸盐和小于0.4%的硫酸盐,以将其pH提高到2-3,从而使氟化钙沉淀为主要成分 ,磷酸钙和硫酸钙作为次要成分沉淀。 所得到的氟化钙沉淀物用生的池塘水洗涤以降低磷酸盐含量并用碳酸铵溶液来降低硫酸盐含量。 以这种方式获得工业上有用的氟石。 然后将低氟上清液与足够的原料池塘水混合以使pH达到1.5-2.0的范围,然后将所得悬浮液在泻湖中保持5-21天,以允许分离二氧化硅。 通过沉降分离后,将含有未沉淀磷酸盐的水返回池塘供进一步使用。 富含二氧化硅的沉淀物可通过离心进一步脱水,并用于磷酸设备以促进氟化物的更好回收。 为了最小化氟化钙产品的硫酸盐污染,可以提供单独的预处理步骤以将池塘水的硫酸盐含量降低至约0.4%。 在该步骤中,加入足够的碳酸钙以将池塘水的pH升高至约2.0,并在足够的老化之后使硫酸钙沉淀,同时在较高pH下沉淀出最少的氟化钙沉淀。 预处理后,通过该过程的第一步处理悬浮液以除去氟化钙。
    • 2. 发明授权
    • Neutralization of cooling pond water in phosphoric acid plants
    • 在磷酸厂中冷却池塘水中和
    • US4472368A
    • 1984-09-18
    • US453213
    • 1982-12-27
    • Padraic S. O'NeillCharles W. WestonKyle D. ClevengerJesse S. Chang
    • Padraic S. O'NeillCharles W. WestonKyle D. ClevengerJesse S. Chang
    • C01B25/01C01D3/02C01B25/16C01F1/00
    • C01B25/01Y10S210/915
    • An economical process for treating the acidic pond water to be used in the internal grinding circuit of a wet process phosphoric acid plant. Water is added to a quantity of a hydratable calcium compound, such as quicklime, to form a slaked lime slurry. A sufficient quantity of the slaked lime slurry is reacted with the acidic pond water to obtain a low fluoride solution having a fluoride content less than about 300 ppm and a pH in the range from about 2.0 to about 3.0, preferentially in the range 2.6-2.8, whereby calcium fluoride is precipitated. The precipitate bearing low fluoride solution is then clarified and the precipitate removed as underflow from the clarifier and transferred to the gypsum pond. In the preferred embodiment, the clarified low fluoride water is fed to the ball mill and is mixed with the phosphate rock being crushed. Removal of fluoride from the pond water solution reduced the "blinding effect" of the fluoride and permits the calcium carbonate in the phosphate rock to neutralized the acidic pond water to minimize corrosion in the mill and elsewhere in the plant. The resulting slurry from the ball mill is about 55% to 65% solids and ranges in pH range from about 5.0 to about 5.5. The phosphate rock slurry is then passed through a hydroclone circuit where the larger (heavier) particles are removed for recycling to the ball mill and the remaining lightweight particles in the rock slurry are processed by phosphoric acid plant.
    • 一种用于处理湿法磷酸装置的内部研磨回路中使用的酸性池塘水的经济方法。 将水加入一定量的可水合的钙化合物,例如生石灰,以形成熟石灰浆料。 将熟化的熟石灰浆料与酸性池塘水反应,得到氟化物含量低于约300ppm,pH在约2.0至约3.0范围内,优选2.6-2.8的氟化物溶液 ,由此使氟化钙沉淀。 然后将含有低氟化物溶液的沉淀物澄清,并从沉淀器中下溢出沉淀物并将其转移到石膏池中。 在优选的实施方案中,将澄清的低氟化物水供给到球磨机中,并与被粉碎的磷酸盐岩混合。 从池塘水溶液中除去氟化物减少氟化物的“致盲效应”,并允许磷酸盐岩中的碳酸钙中和酸性池塘水,以最大限度地减少磨机和工厂其他地方的腐蚀。 来自球磨机的所得浆料为约55%至65%的固体,其范围为约5.0至约5.5的pH范围。 然后将磷酸盐岩浆通过水力旋流回路,其中较大(较重)的颗粒被去除以再循环到球磨机中,并且岩浆中剩余的轻质颗粒由磷酸设备处理。