Exploring the feasibility and influencing factors of phosphorus recovery from phosphorus-rich groundwater based on struvite precipitation methods
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摘要:
磷供应短缺和水体磷污染已成为全球性危机。鸟粪石沉淀法是最为经济有效的磷回收方法，其磷的回收率可以达到95%以上，目前已广泛应用于污水中磷的资源化。天然富磷地下水近年来备受关注，但目前尚未有基于鸟粪石法开展富磷地下水中磷回收的报道。探讨了在富磷、富钙、富铁、富黄腐酸（FA）地下水中利用鸟粪石法在pH值为9.5的环境下回收磷的影响因素与可行性。利用X射线衍射（XRD）、扫描电镜（SEM）和傅里叶变换红外光谱（FTIR）等方法对人工合成地下水与天然地下水开展了研究。结果表明，随着钙浓度增加沉淀中鸟粪石纯度迅速下降到10%以下，XRD图谱中鸟粪石的峰消失，SEM图谱中鸟粪石表面被无定形磷酸钙覆盖，单独添加铁和黄腐酸后鸟粪石的纯度变化较小，SEM图谱显示固体表面出现絮状沉淀。影响因子共存条件下得到的鸟粪石沉淀X射线光谱显示出无规则峰值，傅里叶红外光谱图分别在波数453，720，750，
1608 ，1679 cm−1处的峰消失，表明高浓度的钙能显著抑制地下水中鸟粪石的形成，铁和黄腐酸对鸟粪石形成的影响相对较弱；研究因子的共存会加剧抑制鸟粪石的形成，3个因子共同决定了鸟粪石能否在地下水中有效沉淀。本研究识别了鸟粪石沉淀法回收地下水中磷的影响因素与机制，研究结果将有助于富磷地下水中磷回收策略的制定。Abstract:Objective The global phosphorus (P) supply shortage and water pollution crisis necessitate an urgent shift from simply removing polluted phosphorus to leveraging it as a resource. Among recovery methods, the struvite precipitation method is recognized for its cost-effectiveness and high efficiency, achieving phosphorus recovery rate exceeding 95%. This method has been widely used in the reclamation of phosphorus in sewage. Despite extensive research on naturally P-rich groundwater in recent years, there is a lack of studies focusing on phosphorus recovery using the struvite method.
Methods This study explores the influencing factors and feasibility of employing the struvite method to recover phosphorus from groundwater abundant in phosphorus, calcium, iron, and fulvic acid (FA) at an optimal pH of 9.5. The aim is to develop an integrated phosphorus recycling system for P-rich groundwater and offer constructive suggestions for groundwater phosphorus recycling. Advanced techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared (FTIR) spectroscopy were utilized alongside the molybdenum blue method for phosphoric acid detection, the Nash reagent was used for ammonia nitrogen detection, and Origin 9.0 was used for data visualization. These techniques have been used to thoroughly study both synthetic and natural groundwater.
Results The results show that as calcium concentration increases, the purity of struvite declines rapidly to below 10%, with the struvite peak vanishing in XRD patterns and amorphous calcium phosphate covering struvite surface in SEM patterns. When iron and/or fulvic acid were added individually, the struvite purity remained relatively unchanged. The XRD patterns revealed a weakened struvite peak, while the SEM patterns showed that flocculation precipitation occurred on the solid surface. The X-ray spectra of struvite precipitates obtained under the coexistence of influencing factors showed irregular peaks, with the peaks at 453 cm−1, 720 cm−1, 750 cm−1,
1608 cm−1, and1679 cm−1 disappearing from the FTIR spectra. These results suggest that high calcium ion concentrations significantly inhibit struvite formation in groundwater, whereas iron ions and fulvic acid have minor effects. The coexistence of these factors intensifies the inhibition of struvite formation, ultimately determining whether struvite can be effectively precipitated in groundwater.Conclusion This study identifies the key factors and mechanisms affecting phosphoric recovery from groundwater through struvite precipitation. The insights gained from this research are valuable for formulating effective recovery strategies for phosphorus in P-rich groundwater.
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Key words:
- struvite /
- phosphorus recovery /
- groundwater /
- calcium ion /
- iron ion
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图 1 磷酸盐去除率、氨氮去除率与溶液Mg/P比值（a）和pH值（b）的关系
Figure 1. Relationship between the removal rates of phosphate and ammonia nitrogen and the Mg/P ratio (a) and pH (b) of solutions
图 2 pH=9.5时各影响因素的XRD图谱
a. FA；b. Fe3 +；c. Ca2 +；d. FA与Fe3+、Ca2+耦合；e. Fe3+与FA、Ca2+耦合；f. Ca2+、FA、Fe3+耦合；g. FA、Fe3+和Ca2+共同耦合；h. 天然地下水
Figure 2. XRD patterns for each group of influencing factors obtained at pH 9.5
图 3 在pH =9.5下获得的影响因素的SEM图像
a， b. 鸟粪石；c， d. FA ； e，f. Fe3+；g，h. Ca2+
Figure 3. SEM images of the influencing factors obtained at pH 9.5
图 4 3个影响因素在pH=9.5时的XRD衍射峰强度对比
Figure 4. Comparison of XRD peak intensites at pH 9.5 for the three influencing factors
图 5 在pH =9.5条件下影响因素耦合后析出相的SEM图像
a，b. FA与Fe3+耦合；c，d. FA与Ca2+耦合；e，f. Ca2+与Fe3+耦合；g. FA、Fe3+和Ca2+耦合；h. 天然地下水
Figure 5. SEM images of the precipitates obtained after coupling of influencing factors at pH 9.5
图 6 FA-Fe、FA-Ca、Fe-Ca、FA-Fe-Ca耦合和纯净鸟粪石的FTIR光谱
Figure 6. FTIR spectra of FA coupled with Fe, FA coupled with Ca, Fe coupled with Ca, FA-Fe-Ca coupled, and pure struvite
表 1 不同干扰因素、各干扰因素耦合及地下水实际情况下产生的沉淀物的纯度和粒径
Table 1. Purity and particle size of precipitates generated in the presence of different interfering factors， combination of interfering factors， and actual groundwater
干扰因素 鸟粪石纯度/% 鸟粪石粒径/nm Ca/Mg 1:5 83.45 51.10 1:3 73.88 57.59 1∶1.2 52.22 54.52 2∶1 14.52 57.52 Fe 10 mg/L 91.50 50.04 50 mg/L 77.52 48.27 100 mg/L 44.10 50.65 FA 5 mg/L 74.68 50.52 20 mg/L 78.96 51.12 50 mg/L 72.98 62.43 FA-Fe 耦合 55.98 50.52 FA-Ca 耦合 48.52 60.10 Ca-Fe耦合 43.56 62.50 FA-Fe-Ca 耦合 16.42 63.26 天然地下水 88.0 69.50 
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