\mathrmCO_3^2- 与Ca2+对磷酸铵镁结晶法去除模拟猪场厌氧消化液中磷的影响机制

Influence mechanisms of \bfCO_\bf3^\bf2- and Ca2+ on phosphorus removal of synthetic swine wastewater anaerobic digestate by magnesium ammonium phosphate crystallization

  • 摘要: 为提高养殖废水厌氧消化液中磷的回收效率与产物资源化价值,以模拟猪场厌氧消化液为对象,系统探究了碳酸根(\mathrmCO_3^2- )与钙离子(Ca2+)对磷酸铵镁(MAP)结晶法除磷过程的影响机制。通过批次沉淀实验,结合Visual MINTEQ 3.0热力学模型与X射线衍射分析,揭示了不同pH与镁、氮、磷物质的量比〔n(Mg)∶n(N)∶n(P)〕条件下磷的去除规律与产物特征。结果表明:在pH=9.5、n(Mg)∶n(P)=1.4∶1时,磷去除率超过96%,继续提高pH或n(Mg)∶n(P)对去除率的提升作用不显著。\mathrmCO_3^2- 单独存在对磷去除率(>95%)及MAP晶体纯度影响较小;而Ca2+单独存在则显著改变沉淀产物组成,当n(Mg2+)∶n(Ca2+)=2∶1时,MAP纯度约为66.7%,随着Ca2+浓度升高,产物逐渐转为无定形磷酸钙主导。\mathrmCO_3^2- 与Ca2+共存时的影响与Ca2+单独存在时基本一致,高Ca2+/\mathrmCO_3^2- 背景下虽能维持高磷去除率(≥95%),但产物纯度显著下降。在实际应用中,应根据离子浓度比精确控制镁与磷的物质的量比,以平衡磷的去除率及回收产物的资源价值。

     

    Abstract: To enhance phosphorus recovery efficiency and the resource value of products from swine wastewater anaerobic digestate, this study systematically investigated the influence mechanisms of carbonate (\mathrmCO_3^2- ) and calcium ions (Ca2+) on phosphorus removal via magnesium ammonium phosphate (MAP) crystallization using synthetic swine wastewater anaerobic digestate. Batch precipitation experiments, coupled with Visual MINTEQ 3.0 thermodynamic modeling and X-ray diffraction analysis, were conducted to elucidate the phosphorus removal behavior and product characteristics under different pH conditions and molar ratios of n(Mg)∶n(N)∶n(P). The results indicated that a phosphorus removal rate exceeding 96% was achieved at pH 9.5 with n(Mg)∶n(P) = 1.4∶1; further increases in pH or n(Mg)∶n(P) molar ratio showed no significant improvement in removal efficiency. The presence of \mathrmCO_3^2- alone had minimal impact on phosphorus removal (>95%) and the purity of MAP crystals. In contrast, the presence of Ca2+ alone significantly altered the composition of the precipitates. When n(Mg2+)∶n(Ca2+) = 2∶1, the purity of MAP was approximately 66.7%, and as the Ca2+ concentration increased, the products gradually transitioned to being dominated by amorphous calcium phosphate. The combined influence of \mathrmCO_3^2- and Ca2+ was largely consistent with that of Ca2+ alone. Under high Ca2+/\mathrmCO_3^2- conditions, although a high phosphorus removal rate (≥95%) was maintained, the purity of the product decreased substantially. In practical applications, the Mg∶P molar ratio should be precisely controlled based on the ionic concentration ratios to balance phosphorus removal efficiency and the resource value of the recovered products.

     

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