Resource recovery from vanadium-extracted wastewater and high-magnesium desulfurization wastewater via synergistic magnesium ammonium phosphate precipitation
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摘要: 钒生产企业在钠化提钒和烟气脱硫过程中会产生大量含有高浓度氨氮、六价铬、盐的“三高”型复杂提钒废水与富镁脱硫废水，给资源回收和环境保护带来严峻挑战。传统分质处理模式存在占地面积大、运维成本高等问题。研究提出一种基于磷酸铵镁沉淀的协同处理策略，将其作为前处理，提钒废水提供氮源，富镁脱硫废水提供镁源。结果表明，反应过程中调节pH至9.5，n(Mg):n(N)=1.8，n(P):n(N)=1.5，反应15 min，氨氮和镁的回收率分别高达97.72%和86.62%，沉淀物主要由不含铬的磷酸铵镁（73.24%）和磷酸钾钠镁（23.75%）组成，实现氮、镁资源协同回收。此外，该策略可减少22%～60%化学药剂用量，显著降低占地面积，减轻后续高盐废水的处理负荷，为钒厂废水资源化利用提供了新思路。Abstract: Vanadium production generates significant quantities of “triple-high” complex vanadium-extracted wastewater (high in ammonia-nitrogen, hexavalent chromium, and salt) from sodic roasting vanadium extraction, alongside magnesium-rich desulfurization effluent from flue gas desulfurization. These effluents pose significant resource and environmental challenges. Traditional separate treatment methods for these wastewater face challenges of large land occupation and high maintenance costs. This study proposes a struvite-driven co-treatment strategy aimed at the preliminary treatment process, where vanadium-extracted wastewater serves as the nitrogen source and desulfurization wastewater provides magnesium for struvite precipitation. Under optimal conditions (pH = 9.5, n(Mg):n(N) = 1.8, n(P):n(N) = 1.5, reaction time = 15 min) with in-progress precipitation pH adjustment mode. The process enabled recovery of NH4+–N (97.72%) and Mg2+ (86.62%), and precipitated Cr-free struvite (73.24%) and hazenite (23.75%), highlighting its dual-resource recycling capability. Additionally, the process reduced chemical usage by 22%-60% and minimized land occupation, thereby reducing the treatment load of subsequent high-salt wastewater. This research provides a new and efficient strategy for the resource utilization of wastewater generated by vanadium plants.
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图 1 pH值及其调节方式对NH4+−N、Ca2+、 Mg2+、 Cr(VI)浓度以及沉淀质量的影响
(a) NH4+−N；(b) Ca2+； (c) Mg2+；(d) Cr(VI)浓度；(e)沉淀质量
Figure 1. Effects of pH and its adjustment mode on the concentrations of NH4+−N, Ca2+, Mg2+, Cr(VI), and sediment mass
图 2 n(Mg):n(N)对NH4+−N、Ca2+、Mg2+、Cr(VI)浓度以及沉淀质量的影响
Figure 2. Effects of n(Mg):n(N) on the concentrations of NH4+−N, Ca2+, Mg2+, Cr(VI), and sediment mass
图 3 不同n(Mg):n(N)下得到沉淀物的XRD图谱对比
Figure 3. XRD patterns of precipitates obtained at different n(Mg):n(N)
图 4 n(P):n(N)对NH4+−N、Ca2+、Mg2+、Cr(VI)浓度以及沉淀质量的影响
Figure 4. Effects of n(P):n(N) on the concentrations of NH4+−N, Ca2+, Mg2+, Cr(VI), and sediment mass
图 5 不同n(P):n(N)下得到沉淀物的XRD图谱对比
Figure 5. XRD patterns of precipitates obtained at different n(P):n(N)
图 6 反应时间对NH4+−N、Ca2+、Mg2+、Cr(VI)浓度以及沉淀质量的影响
Figure 6. Effects of reaction time on the concentrations of NH4+−N, Ca2+, Mg2+, Cr(VI), and sediment mass
图 8 回收产物的SEM和EDS图
Figure 8. SEM and EDS images of the obtained products
(a) SEM；(b)～(g) EDS
表 1 提钒废水主要参数
Table 1. Key parameters of vanadium-extracted wastewater
Parameter Average value (mg/L, except pH) pH 2.46 Cr(VI) 1500 N 2850 Si 3.92 V 29.9 P <0.01 Ca 47 
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表 2 富镁脱硫废水主要参数
Table 2. Key parameters of high-magnesium desulfurization wastewater
Parameter Average value (mg/L, except pH) pH 7.50 Mg2+ 34820 Ca2+ 480 K+ 9370 Na+ 1560 Cl– 18920 SO42− 130170
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表 3 几种常见组合的原料成本比较
Table 3. Comparison of raw material costs for several common combinations
Combination Mg source Unit price of Mg source (CNY/kg) Input cost (CNY/kg MAP) Cost saving/% A MgO 180 176.36 22 B MgCl2·6H2O 62 205.01 33 C Mg(OH)2 670 346.69 60 D MgSO4·7H2O 46 225.82 39 E High-magnesium desulfurization wastewater 0 137.53 Note: Prices were obtained from www.reagent.com and reflect quotations for 500 g bottles of chemical pure (CP) grade, as of January 2025.
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