硼酸已於民生工業中扮演著不可或缺的角色，近年來又隨著高科技產業製程上的需求及化學儲氫材料的使用，產生的含硼廢水需被審慎對待。本研究即針對含硼廢水分別以鈣鹽及鋇鹽做為沉澱劑、雙氧水做為過氧劑，嘗試利用新的化學過氧沉澱(COP)技術取代傳統化學沉澱(CP)，以提升除硼效率。接著配合COP，引進流體化床均質顆粒化(FBHG)技術，以產生過硼酸鈣或過硼酸鋇均質顆粒，達到同時改善水質並資源化有價過硼酸鹽的效果。
於COP批次測試系統中，乃針對1000 mg-B/L分別探討pH、Me/B、H2O2/B等變因，研究結果發現相較於金屬離子濃度，H2O2濃度對除硼效果有較顯著的影響，當H2O2/B=Me/B=1且pH在10~11間時有最佳除硼效果。Ca鹽系統中硼的去除率大於85％，可使硼濃度降至129 mg-B/L；而Ba鹽系統中硼的去除率更大於95％，可降至38 mg-B/L。
於FBHG連續測試系統中，當進料為300 mg-B/L時，實驗結果顯示鈣鹽及鋇鹽系統皆可長出均質顆粒，且Ba鹽系統的除硼效果優於Ca鹽系統，與COP批次測試結果吻合。Ba鹽系統可在上流速度為20 m/hr、H2O2/B=1.5，pHe=9的條件下達到60 %的結晶率，反應器之槽體負荷約落於1500~1800 g-B/hr•m2間，且在調整pH值並經過沉澱槽後，可再提升去除率最高至85 %。
最後，在產品的鑑定方面，FBHG產生的顆粒經過Raman鑑定其含有O-O官能基，然而XRD顯示無論是COP汙泥或FBHG顆粒皆無結晶相。若將汙泥鍛燒至700 °C，則可用XRD及Raman證明高溫後的產品為偏硼酸鈣及偏硼酸鋇。且由TGA及DSC可了解產品之熱性質，包含水的蒸發、氧氣的釋出等變化，最後綜合以上分析結果可推測顆粒的化學式應為BaB2O4(OH)4及Ca(BO3)2 • nH2O。

This study investigated a chemical oxo-preceipitation (COP) process for the treatment of the synthetic boric acid wastewater. COP combined the oxidant treatment and chemical precipitation using different metal salts (CaCl2 and BaCl2) for boron removal. Metal borate which was of high purity and single compound could be recovered by fluidized-bed homogeneuous Granulation (FBHG) process without adding seed materials.
In COP stage, the molar ratio of metal to boron (Me/B), H2O2 to boron (H2O2/B) and pH were the primary variables for optimizing the treatment of 1000 mg-B/L synthetic boric acid solution. At pH around 10-11, the boric acid concentration could be substantially redued to 129 and 38 mg-B/L using CaCl2 and BaCl2 as precipitants, respectively, through the COP conditions of H2O2/B=1 and Me/B=1. Besides, H2O2 dosage affected the COP efficiency on boron removal more than precipitant did. In FBHG stage, the optimal parameters (U=20 m/hr、H2O2/B=1.5、Ba/B=2、pHe=9) could successfully recover the spherical particles of barium peroxoborate. For a feed level of 300 mg-B/L, 60% of crystallization ratio and 85% of removal efficiency were obtained at pH 10.75.
The particles from FBHG were characterized by SEM, XRD, Raman, and thermal analysis (TGA and DSC). The peroxide (O-O) functional group in particles could be monitored by Raman spectroscopy. The XRD patterns indicate that the FBHG products had a poor crystallinity; however, these borate compounds showed clear characteristic peaks that were well fitted with calcium metaborate (CaB2O4) and barium metaorate (BaB2O4) phase after 700 °C calcination. Water evaporation and oxygen released during the thermal decomposition could be observed through TGA and DSC analysis. According to the analytical results, the FBHG products using calcium ion and barium ion as precipitants were supposed to be calcium peroxoborate (Ca(BO3)2 • nH2O) and barium peroxoborate (BaB2O4(OH)4), respectively.

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