含鋯廢水若僅以污染物去除為目標，雖可降低水相中鋯濃度，但若能進一步將鋯轉化為可分離與回收之固體顆粒，則更具資源化應用價值。目前含鋯廢水常見處理方式包括溶劑萃取、離子交換、吸附及化學沉澱等方法，其中化學沉澱法因操作簡單、反應快速且可處理較高濃度金屬廢水，為常見之處理方式。然而Zr(IV) 於水溶液中具有強烈水解與聚合傾向，當pH升高時容易快速形成氫氧化鋯或水合氧化鋯沉澱，使系統進入高過飽和狀態，導致大量均相成核、細微非晶沉澱或膠狀固體生成，造成固液分離困難、污泥化及顆粒化回收不易。
為改善上述問題，本研究以合成含鋯廢水為對象，應用流體化床均質結晶技術進行鋯去除與顆粒化回收，並導入碳酸根作為化學調控因子，探討其對鋯水相物種、溶解度、過飽和度與結晶回收行為之影響。研究首先以瓶杯試驗(Jar-test)評估 pH、反應時間及 [CO32−]/[Zr(IV)] 莫耳比對鋯沉澱行為之影響，再將適宜條件應用於連續式流體化床均質結晶系統，探討不同操作變因對總去除率、結晶率、溶解態殘留鋯濃度及總殘留鋯濃度之影響。
實驗結果顯示，未添加碳酸根時鋯於pH 7–12範圍內皆可快速沉澱並達高去除效果，但易受快速水解與高過飽和度控制而形成細微固體。加入適量碳酸根後，碳酸根可與Zr(IV)形成碳酸或羥基碳酸錯合物，提高鋯之溶解度並降低過飽和度，使沉澱生成速率較為緩和，有利於固相於床層中截留、聚集與成長；但碳酸根過量時，鋯會過度穩定於水相中，導致去除與回收效率下降。流體化床均質結晶結果顯示，在適當操作條件下，初始鋯濃度為500 mg-Zr/L之合成廢水可達99%以上之總去除率，結晶率最高約為95%。本研究證實碳酸根可作為鋯沉澱路徑與過飽和度之調控因子，結合流體化床均質結晶技術可提升含鋯廢水顆粒化回收之可行性。

Zirconium-containing wastewater treatment should not only remove dissolved zirconium but also convert it into recoverable solid particles. Chemical precipitation is commonly used because of its simple operation and rapid reaction. However, Zr(IV) strongly hydrolyzes and polymerizes in aqueous solution. When pH increases, zirconium easily forms zirconium hydroxide or hydrous zirconium oxide precipitates, causing high supersaturation, homogeneous nucleation, fine amorphous solids, and gel-like precipitates. These properties make solid-liquid separation and particle recovery difficult.
This study applied fluidized bed homogeneous crystallization (FBHC) to recover zirconium from synthetic wastewater, with carbonate introduced as a chemical regulating agent. Jar-test experiments were conducted to evaluate the effects of pH, reaction time, and [CO32−]/[Zr(IV)] molar ratio. The selected conditions were then applied to a continuous FBHC system to investigate total removal efficiency, crystallization ratio, and residual zirconium concentrations.
Results showed that zirconium could be rapidly removed at pH 7–12 without carbonate addition, but fine precipitates were easily formed. Appropriate carbonate addition increased zirconium apparent solubility and reduced effective supersaturation, improving particle retention and growth. Under suitable conditions, wastewater containing 500 mg-Zr/L achieved over 99% total removal and a maximum crystallization ratio of approximately 95%.

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