CO32-与Ca2 对磷酸铵镁去除模拟猪场厌氧消化液中磷的影响机理

The effects mechanism of CO32- and Ca2 on phosphorus removal of synthetic anaerobic digestion of swine wastewater by crystallization of magnesium ammonium phosphate

  • 摘要: 摘要  以模拟猪场废水厌氧消化液为处理对象,进行了磷酸铵镁(MAP)沉淀除磷小试实验,应用修正的Visual MINTEQ 3.0模型分析了CO32-、Ca2+以及其共存对MAP沉淀反应的影响机理;利用X射线衍射仪(XRD)对沉淀产物进行了表征。结果表明,较高pH值和初始n(Mg):n(N):n(P)摩尔比有利于MAP结晶反应,但当pH≥9.5,初始n(Mg):n(P)≥1.4:1时,对提高P的去除率贡献不明显;P的沉淀量与溶液pH值呈二项式函数关系。当pH=9.5时,CO32-单独存在会略微降低磷的去除率,但对MAP的结构和纯度影响不大;Ca2+单独存在可提高磷的去除效率;Ca2+浓度高低对回收产物的组成和MAP的纯度均有明显影响,当n(Mg): n(Ca)=2:1时,沉淀中组成成分主要为MAP,其纯度约为66.7%,随着Ca2+浓度增大,反应将生成无定形的磷酸钙(ACP)沉淀。CO32-和Ca2+共存对沉淀反应过程的影响与Ca2+单独存在时较为一致,在n(Mg):n(CO3):n(Ca)=2:1:1和1:1:1时,沉淀产物中未出现碳酸钙(CaCO3)沉淀;但当n(Mg):n(CO3):n(Ca)=1:2:2时,沉淀产物可能包含CaCO3沉淀,但由于含量较低,其衍射峰并未在XRD谱图中明显表现。

     

    Abstract: Abstract   Using synthetic anaerobic digestion of swine wastewater, bench-scale experiments were carried out. The influence mechanism of carbonate (CO32-), calcium (Ca2+) as well as the coexistence of CO32- and Ca2+ on magnesium ammonium phosphate (MAP) precipitation reaction was analyzed by the modified Visual MINTEQ 3.0. The composition of the obtained precipitate was analyzed and characterized by X-ray Diffraction (XRD). The results showed that higher pH value and initial n(Mg):n(N):n(P) molar ratio were beneficial to MAP precipitation. However, with pH value≥9.5 and the initial n(Mg):n(P) molar ratio≥1.4:1, these two factors had negligible effects on the improvement of phosphate removal rate. Precipitated P is a binomial function of the solution pH value. At pH 9.5, the presence of CO₃²⁻ alone marginally reduced phosphorus (P) removal efficiency, while exhibiting no discernible impact on the crystalline structure or purity of MAP product. The single existence of Ca2+ increased P removal efficiency. The concentrations of Ca2+ obviously affected the components of the precipitate and the purity of MAP. At the condition that n(Mg): n(Ca)=2:1, MAP became the main component of the precipitate, with the purity of MAP be about 66.7%. Amorphous calcium phosphate(ACP) was produced with the concentration of Ca2+ increased. The effects of coexisting CO32- and Ca2+ on the precipitation process was consistent with the single existence of Ca2+. CaCO₃ precipitation was absent at Mg:CO₃:Ca molar ratios of 2:1:1 and 1:1:1. At a 1:2:2 ratio, CaCO3 may have formed, but its concentration was below the XRD detection limit, precluding definitive identification.

     

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