多形貌蛋壳基羟基磷灰石对好氧颗粒污泥冷冻复苏及结构稳定性的影响

Effect of multi-morphology eggshell-based hydroxyapatite on the freezing recovery and structural stability of aerobic granular sludge

  • 摘要: 实现冷冻储存好氧颗粒污泥性能快速复苏与维持其长期稳定运行,是保障废水处理效能的关键。本研究以废弃鸡蛋壳为前驱体,采用溶剂热法合成了针尖状、花瓣状及针尖-花瓣状羟基磷灰石,并借助SEM-EDS、比表面积(BET)、XRD等表征分析其理化性质。在3组网板序批式反应器(SBR,A0组:针尖状,A1组:花瓣状,A2组:针尖-花瓣状)中接种冷冻好氧颗粒污泥与0.3 g/L羟基磷灰石,系统探究了羟基磷灰石对冷冻好氧颗粒污泥启动再生、降解污染物效能与胞外聚合物(EPS)分泌的影响,以及初步阐明了针尖-花瓣状羟基磷灰石介导好氧颗粒污泥再生的内在机制。结果表明,针尖状、花瓣状及针尖-花瓣状羟基磷灰石的微观形貌分别呈现细长尖锐状、蓬松多孔团聚体和复合分级结构,比表面积分别为17.414222.868628.1209 m2/g,平均Zeta电位分别为−8.64、−5.64和−4.53 mV,针尖-花瓣状羟基磷灰石兼具高孔隙率、高比表面积与微弱负电性。羟基磷灰石的投加可增大再生颗粒污泥粒径、促进EPS分泌及重构颗粒骨架结构,A0、A1和A2组污泥平均粒径分别达到1.83±0.05 mm、2.02±0.02 mm和2.25±0.03 mm,对应EPS含量分别约为80.31、99.80、109.28 mg/g,污泥颗粒结构稳定性显著提升;在SBR运行过程中,A0组对废水中COD、NH4+-N和TP的平均去除率分别为82.10%、71.93%和60.36%,A1组相应为85.15%、71.52%和64.44%,A2组相应为88.12%、76.51%和70.01%,针尖-花瓣状羟基磷灰石强化了污染物的去除。依托材料吸附启动、EPS调控与颗粒结构重构及体系pH自稳与长期稳定运行三重协同作用机制,可实现冷冻好氧颗粒污泥高效快速启动,完成污泥再凝聚与成型。本研究验证了引入不同形貌羟基磷灰石介导冷冻好氧颗粒污泥复苏的可行性。该策略不仅改善了颗粒污泥复苏阶段结构易溃散、生物活性恢复滞后等痛点,还能为好氧颗粒污泥工艺稳定运行提供参考价值。

     

    Abstract: The key to ensure the treatment efficiency of wastewater is to realize the rapid recovery of the performance of frozen storage aerobic granular sludge and maintain its long-term stable operation. In this study, needle-like, petal-like and needle-petal-petal-like hydroxyapatite were synthesized by solvothermal method using waste egg shells as precursors. The physicochemical properties of these samples were characterized by SEM-EDS, BET, XRD, etc. Frozen aerobic granular sludge was inoculated and 0.3 g/L hydroxyapatite was added in a three-plate sequencing batch reactor (SBR, A0 group: needle tip shape, A1 group: petal shape, A2 group: needle tip-petal shape). The effects of hydroxyapatite on the start-up regeneration, pollutant degradation efficiency and extracellular polymer (EPS) secretion of frozen aerobic granular sludge were systematically investigated. At the same time, the internal mechanism of needle-petal hydroxyapatite-mediated aerobic granular sludge regeneration was preliminarily elucidated. The results show that the micro-morphology of needle-like, petal-like and needle-petal-petal-like hydroxyapatite presents slender and sharp, fluffy porous aggregates and composite hierarchical structure, respectively. The specific surface areas were 17.4142, 22.8686 and 28.1209 m2/g, respectively, and the average zeta potentials were −8.64, −5.64 and −4.53 mV, respectively. Tip-petal hydroxyapatite has high porosity, high specific surface area and weak negative charge. The addition of hydroxyapatite can increase the particle size of the regenerated granular sludge, promote the secretion of EPS, and reconstruct the particle skeleton structure. The average particle sizes of sludge in A0, A1 and A2 groups reached 1.83 ± 0.05 mm, 2.02 ± 0.02 mm and 2.25 ± 0.03 mm, respectively, and the corresponding EPS contents were about 80.31, 99.80 and 109.28 mg/g, respectively. The stability of sludge particle structure was significantly improved. During the operation of SBR, the average removal rates of COD, NH4+-N and TP in the wastewater of A0 group were 82.10%, 71.93% and 60.36%, respectively. A1 group was 85.15%, 71.52% and 64.44%. A2 group was 88.12%, 76.51% and 70.01%. Pin-tip-petal hydroxyapatite enhanced the removal of pollutants. Based on the triple synergistic mechanism of material adsorption start-up, EPS regulation and particle structure reconstruction, system pH self-stabilization and long-term stable operation, the efficient and rapid start-up of frozen aerobic granular sludge can be realized, and the sludge re-agglomeration and molding can be completed. This study verified the feasibility of introducing hydroxyapatite with different morphologies to mediate the recovery of frozen aerobic granular sludge. This strategy not only improves the pain points such as easy disintegration of granular sludge structure and lagging recovery of biological activity in the recovery stage, but also provides reference value for the stable operation of aerobic granular sludge process.

     

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