酸浸猪粪磷形态转变及强化蓝铁矿回收的研究

    Phosphorus Transformation and Vivianite Recovery Enhancement from Acid Leaching Pig Manure

    • 摘要: 猪粪因其磷含量高而成为具有前景的磷回收原料。为了提高猪粪中磷的回收效果, 考察了硫酸(H2SO4)、盐酸(HCl)、草酸(H2C2O4)和抗坏血酸(C6H8O6)4种浸提剂的酸浸浓度、酸浸时间以及液固比对猪粪释磷效果的影响, 以及对砷(As)、铬(Cr)、铜(Cu)和锌(Zn)等重金属元素浸出行为的影响; 通过C-J连续提取法对比分析4种酸处理前后的磷形态, 探明猪粪中磷形态转化规律; 最后探讨了二价铁(Fe2+)诱导结晶生成蓝铁矿的可行性。结果表明, H2C2O4酸浸释磷性能优于H2SO4和HCl, 显著优于C6H8O6。猪粪样品经4种提取液酸浸后, 重金属元素释出量大小为Zn>Cu>As>Cr; 与H2SO4和HCl相比, H2C2O4对重金属元素的浸出量更低。H2SO4、HCl、H2C2O4和C6H8O6对固相磷中铝结合态磷(Al-P)和钙结合态磷(Ca-P)均具有较优的转化效果, 转化率>80%;而对于固相磷中的交换态磷(Ex-P)、液相磷中的颗粒态磷(PP)和溶解性还原磷(RDP), 与其他3种酸相比, H2C2O4对其具有更高的转化效率。经综合比选, 明确H2C2O4为猪粪磷的最佳浸提剂。在H2C2O4浓度为0.10 mol·L-1、酸浸时间为60 min和液固比为50 mL·g-1条件下处理猪粪, 液相中可溶性正磷酸盐(Ortho-P)含量从188 mg·L-1提高到882 mg·L-1, 释磷量从9.42 mg·g-1提升到44.1 mg·g-1, 效率提升369%。采用Fe2+诱导结晶生成蓝铁矿回收上清液中的磷, 通过X射线衍射仪(XRD)、X射线光电子能谱(XPS)和扫描电镜(SEM)等表征手段得出, 反应合成的磷回收产物为纯度较高的蓝铁矿。研究成果可为猪粪中磷回收率和回收产物价值的提升提供依据。

       

      Abstract: Pig manure has been recognized as a potent source for phosphorus recovery due to its substantial phosphorus content. To optimize the efficiency of phosphorus extraction, the effects of various acid types (sulfuric acid-H2SO4, hydrochloric acid-HCl, oxalic acid-H2C2O4, and ascorbic acid-C6H8O6), concentration of acids, duration of leaching, and the liquid-to-solid ratio were thoroughly examined. Additionally, the leaching process was monitored for the release behavior of heavy metals such as As, Cr, Cu, and Zn. The transformation mechanisms of phosphorus speciation before and after treatment were analyzed using the C-J extraction method. The potential of Fe2+-induced crystallization to produce vivianite, a phosphorus recovery method, was also explored. Results indicate that H2C2O4 was superior in phosphorus release efficiency compared to H2SO4, HCl, and C6H8O6. The sequence of heavy metal release during the acid leaching was Zn > Cu > As > Cr, with the H2C2O4 group showing a significantly lower heavy metal release rate than the H2SO4 and HCl groups. In terms of phosphorus conversion in solid forms (Al-P and Ca-P), all acid treatments achieved over 80% conversion efficiency. Notably, the H2C2O4 treatment showed enhanced conversion rates for Ex-P in solid phosphorus, as well as for particulate phosphorus (PP) and readily dispersible phosphorus (RDP) in the liquid phase. The optimal conditions for phosphorus extraction using H2C2O4 were determined to be a concentration of 0.10 mol·L-1, a leaching duration of 60 minutes, and a liquid-to-solid ratio of 50 mL·g-1. Under these conditions, the soluble orthophosphate (Ortho-P) concentration in the liquid phase soared from 188 mg·L-1 to 882 mg·L-1, while the phosphorus release content dramatically increased from 9.42 mg·g-1 to 44.1 mg·g-1, marking a 369% enhancement in phosphorus release efficiency. The method of employing Fe2+-induced crystallization to recover phosphorus from the leachate treated with H2C2O4 yielded high-purity vivianite has been confirmed by comprehensive analyses including X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy (SEM). These findings lay a solid foundation for improving both the phosphorus recovery rate and the value of products derived from pig manure.

       

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