• 关键词：磷霉素制药废水  湿式氧化  磷酸盐固定化  有机磷  磷酸铵镁  磷酸钙  磷回收

• 基金项目：水体污染控制与治理科技重大专项课题(No.2008ZX07208-003); 国家自然科学基金项目(No. 50678162, 51078339)

• 邱光磊
• 1. 中国环境科学研究院, 城市水环境研究室, 北京 100012;
  2. 北京师范大学, 水科学研究院, 北京 100875

• 宋永会
• 1. 中国环境科学研究院, 城市水环境研究室, 北京 100012;
  2. 北京师范大学, 水科学研究院, 北京 100875

• 曾萍
• 中国环境科学研究院, 城市水环境研究室, 北京 100012

• 肖书虎
• 中国环境科学研究院, 城市水环境研究室, 北京 100012

• 段亮
• 中国环境科学研究院, 城市水环境研究室, 北京 100012

• 彭剑峰
• 中国环境科学研究院, 城市水环境研究室, 北京 100012

• 袁鹏
• 1. 中国环境科学研究院, 城市水环境研究室, 北京 100012;
  2. 北京师范大学, 水科学研究院, 北京 100875

• 摘要：采用湿式氧化-磷酸盐固定化组合工艺处理COD为72750 mg · L^-1、总有机磷(TOP)为8225 mg · L^-1的磷霉素制药废水并对废水中磷进行资源化回收.首先,采用湿式氧化工艺,利用分子氧作为氧化剂,将废水中有机磷转化成无机磷酸盐,分别考察了反应温度、氧分压和废水初始pH值对湿式氧化处理效果的影响,结果显示:在反应温度200 ℃、氧分压为1.0 MPa、废水初始pH值为11.2的条件下,湿式氧化工艺可实现废水中COD去除率57%、TOP去除率99%以上,高反应温度、高氧分压以及高废水初始pH值对COD和TOP的去除有利.采用磷酸钙(CP)沉淀和磷酸铵镁(MgNH₄PO₄·6H₂O, MAP)结晶方法,对湿式氧化处理后废水中磷酸盐进行固定化回收,考察了不同Ca²⁺/PO₄^3-摩尔比以及Mg²⁺/NH₄⁺/PO₄^3-摩尔比条件下,磷酸盐固定化工艺对湿式氧化处理后磷霉素废水中磷的回收效果,结果显示:在Ca²⁺/PO₄^3-摩尔比2 ∶ 1以及Mg²⁺/NH₄⁺/PO₄^3-摩尔比1.1 ∶ 1 ∶ 1,废水PO₄^3--P浓度9500 mg · L^-1条件下,CP沉淀和MAP结晶工艺均可以实现磷酸盐固定化回收率99.9%以上,出水PO₄^3--P浓度低于5.0 mg · L^-1.采用扫描电子显微镜(SEM)和X射线衍射(XRD)对固定化磷回收产物进行了表征,结果表明回收产物分别为具有较高纯净度的MAP和掺杂有一定量无定形磷酸钙的羟基磷灰石(Ca₅(PO₄)₃OH, HAP).

• Abstract：Hybrid wet air oxidation-phosphate immobilization was applied to fosfomycin wastewater treatment and phosphorus recovery. The chemical oxygen demand (COD) and total organic phosphorus (TOP) concentrations of the wastewater were 72750 mg · L^-1 and 8225 mg · L^-1, respectively. Firstly, O₂ was used as oxidant in the wet air oxidation process to break down and transform concentrated and refractory organic phosphorus substances into phosphate, and the effects of reaction temperature, oxygen partial pressure and initial wastewater pH value were studied. The results showed that, at a reaction temperature of 200 ℃, an oxygen partial pressure of 1.0 MPa, and initial pH value of 11.2, 99% TOP and 57% COD removal was achieved after reaction for 180 min. High reaction temperature, oxygen partial pressure and initial pH value were favorable for TOP conversion and COD removal. Subsequently, calcium phosphate (CP) precipitation and magnesium ammonium phosphate (MAP) crystallization were used for phosphorus recovery. The effect of the phosphate immobilization processes was studied under different Ca²⁺/PO₄^3- and Mg²⁺/NH₄⁺/PO₄^3- molar ratios. The results showed that, at 2 ∶ 1 Ca²⁺/PO₄^3- and 1.1 ∶ 1 ∶ 1 Mg²⁺/NH₄⁺/PO₄^3- molar ratios, both CP and MAP processes could successfully remove and recover phosphorus and the recovery efficiencies were both above 99.9% with less than 5.0 mg · L^-1 PO₄^3--P left in the solutions. The recovered solids were detected and analyzed by scanning electron microscope (SEM) and X-ray diffraction (XRD). For the MAP process, the product was magnesium ammonium phosphate with high purity, and for CP process, the product was hydroxyapatite mixed with amorphous calcium phosphate.

• Key words：fosfomycin pharmaceutical wastewater  wet air oxidation  phosphate immobilization  organic phosphorus  magnesium ammonium phosphate  calcium phosphate  phosphorus recovery

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