鸟粪石结晶法回收猪粪废水厌氧膜出水中磷的研究

采用厌氧膜生物反应器(AnMBR)处理猪粪废水时,发现消化液膜出水可发生自结晶沉淀反应,生成类似鸟粪石的含氮磷沉淀。试验通过控制初始pH使猪粪废水厌氧膜出水发生自结晶沉淀反应,考察了初始pH(8、9、10)对沉淀物组分及形态的影响。结果表明:初始pH为8、9、10时,磷去除率分别为30.8%、67.6%及87.7%;p H从8提高到9时,沉淀物中鸟粪石晶体的粒径变大且形态更完整;而pH为10时,颗粒较小且含钙沉淀较多;进一步分析各条件下沉淀物的晶体组分可知,初始pH为8、9时,沉淀物中晶体的主要成分为鸟粪石,而初始pH为10时,沉淀物中存在大量的含钙沉淀。因此,在该试验条件下,采用鸟粪石结晶法从该猪粪废水厌氧膜出水中回收磷的最佳初始pH为9。     

利用水通道蛋白正渗透膜浓缩生活污水

为从生活污水中回收水资源并同时减少后续处理的反应器容积,本研究采用水通道蛋白正渗透膜对生活污水进行浓缩,并探究不同汲取液对生活污水的浓缩效果和膜污染的影响.在污水体积浓缩至初始的1/10时,氮、磷等浓度浓缩倍数仅为1~3左右,而有机物和金属离子浓度浓缩倍数约为4~7,浓缩后污水COD/TN从2.9增至10.9,生物脱氮潜力明显提高.由于汲取液的盐反向扩散和原料液中污染物浓度的升高,高离子强度是影响污染物截留率的重要原因.浓缩时采用高浓度汲取液会导致膜表面出现结垢,膜污染严重.采用MgCl₂作为汲取液可有效减轻浓缩过程中的盐度累积,且Mg²⁺的作用还可促进微生物活性,但这也可能导致水通道蛋白的分解.     

鸟粪石法回收废水中磷的沉淀物的组成和晶形

利用镁盐为沉淀剂,以磷酸铵镁沉淀的形式回收模拟废水中的磷.采用扫描电镜和X射线衍射对生成的沉淀物的晶形进行表征,利用ICP和化学分析方法测定沉淀物的组成.并结合饱和度的计算对回收的沉淀物的晶形和纯度进行研究.结果显示:沉淀物为斜方型晶体时才是纯的鸟粪石.针形晶体不是纯的鸟粪石;沉淀物的晶形与溶液的初始饱和度有一定的关系.当溶液的初始饱和度较低时.不管pH或镁或氨氮的浓度在一定范围如何变化,其沉淀物都为斜方形晶体;当溶液的初始饱和度高过一定程度后,其沉淀物中都会出现针形的晶体,且不同条件下所生成的针形晶体的x射线衍射峰都与磷酸镁的特征峰有很好的对应关系,说明针形晶体与磷酸镁有一定的关联.     

膜过滤耦合电化学强化废水中磷回收效能

提出了一种膜过滤耦合电化学非均相沉淀的新型磷回收工艺对含磷废水进行处理,探究不同膜通量、电流密度、磷初始浓度及极性反转时间对磷去除和回收的影响。结果表明:在磷初始浓度为5 mmol/L、膜通量为22.1 L/(m2·h)和电流密度为20 A/m2的条件下,磷平均去除率为92.0%,产物的主要成分为鸟粪石。在flow-through操作模式下,不同磷初始浓度对磷去除效果无明显影响。当系统连续流运行时,每隔4 h极性反转6 min可使反应器磷去除与回收性能处于相对较优水平,磷去除率维持在90%左右。     

摩尔配比对MAP沉淀法回收模拟废水中磷的影响

以磷浓度50mg/L的实验室模拟废水为研究对象,考察了以鸟粪石(MAP)形式回收磷的最佳摩尔配比,并借助X-衍射(XRD)对不同摩尔配比条件下得到的沉淀物进行分析。试验结果表明,在pH=9.5时,以鸟粪石形式回收磷的最佳Mg:N:P=4:1.6:1。对沉淀物的XRD分析发现,在pH=9.5,当固定Mg:P=1.6时,N:P=1时沉淀物中基本不含MAP,当N:P=2时,生成的沉淀物中混有少量的副产物Mg(3PO)42,当N:P2时则生成较纯的MAP;当固定N:P=4时,Mg:P=2是生成较纯的MAP的临界值,超过此比例则生成副产物Mg(3PO)42;当反应按照理论配比投加氨氮和镁盐时,所得产物基本不是MAP,而是副产物Mg(3PO)42。故鸟粪石沉淀结晶反应中应尽量提高氨氮配比,并避免投加过量的镁盐,以保证回收产物的纯度。     

基于污泥减量的鸟粪石回收低浓度氮磷影响因素研究

针对三峡库区城市污水氮磷浓度较低的特点,结合城市污水处理旁路污泥减量技术研究,探索了利用鸟粪石结晶沉淀法回收城市污水中氮磷的可行性及影响因素。研究结果表明:低氮磷浓度时,鸟粪石结晶回收氮磷的规律与国内外已有的针对高浓度氮磷的研究规律不同,当污泥厌氧减量池中磷酸盐质量浓度为30～60 mg/L(约为1～2mmol/L)时,在pH值为10.0～10.5,c(Mg2+)∶c(NH 4+)∶c(PO34-)为1∶1.6∶1,反应时间为25 min,搅拌强度在200 r/min的条件下,通过鸟粪石沉淀反应磷去除率可达50%～75%,氮的去除率最高可达51%。     

MAP沉淀法目标产物最优形成条件及分析方法

为了确定鸟粪石(MAP：MgNH₄PO₄·6H₂O)形成的最优条件,引入化学剖析法,利用酸溶液将鸟粪石沉淀法中所得沉淀物溶解后进行相应的元素分析;提出一种根据沉淀物中的NH⁺₄-N含量间接计算确定鸟粪石含量(即纯度)的分析方法.根据这种计算分析方法,分别得出了不同pH条件下以自来水(主要为地下水)和超纯水作为溶剂所合成的鸟粪石纯度,并对pH和Ca²⁺在鸟粪石形成过程中的影响进行了评估.结果表明,该计算分析方法能够有效实现对MAP沉淀法目标产物的定量分析,弥补了国内外目前普遍依靠XRD技术定性判断所得沉淀物中鸟粪石是否存在的缺陷.以超纯水作为溶剂时,使鸟粪石纯度>90%的最佳pH范围在7.5～9.0,而以自来水为溶剂时,获得相同鸟粪石纯度最佳pH范围则是7.0～7.5.实际污水中常常含有相当数量的Ca²⁺,实施碱性条件(pH>8.0)的MAP沉淀势必大幅降低鸟粪石的纯度.因此,对实际污水回收磷而言,MAP沉淀法的最优pH条件应控制在中性范围(<8.0)以内.     

鸟粪石结晶法回收氨氮影响因素的研究

为了预处理化工厂的高氨氮废水,采用向废水中投加Na2HPO.412H2O和MgCl.26H2O生成磷酸铵镁(鸟粪石)的方法,以去除其中的高浓度氨氮同时获得缓释肥鸟粪石。试验以模拟氨氮废水为研究对象,研究了鸟粪石结晶法回收氨氮的影响因素:反应时间、氨氮初始浓度、pH值、磷酸盐与镁盐投加量对高氨氮废水的去除效果,然后进行不同影响因素的试验,确定了氨氮去除的最佳工艺条件。研究结果表明,鸟粪石结晶法回收氨氮的最佳工艺条件为:反应时间10 min,pH值为9,NH4-N:PO4-P:Mg摩尔比为1:1.05:1.15,NH4-N、PO4-P与Mg的去除率分别为91.52%、99.58%与90.52%;残余浓度分别为90.87、4.96与174.1 mg/L,加入的磷几乎全部回收,无二次污染。预处理的废水进入污水处理厂进一步深度处理。     

鸟粪石法回收养猪废水中磷时pH对沉淀物组分的影响

采用鸟粪石沉淀法对养猪废水中的磷进行回收,应用红外光谱和X射线衍射法,并结合物料衡算研究pH变化对沉淀物组分的影响.结果表明,当pH由8.0升至9.0时,磷去除率从85%增加到94%;pH在9.0～11.0范围,磷去除率稳定在94%左右;当pH升高至12.0,磷去除率急剧下降至70％.沉淀物组分为鸟粪石(MgNH₄PO₄·6H₂O)、 钾型鸟粪石(MgKPO₄·6H₂O)、 Ca₃(PO₄)₂·xH₂O和Mg(OH)₂,不含有硫酸盐和碳酸盐.当pH<9.0,沉淀物组分主要为鸟粪石;pH在9.0～10.0范围时,鸟粪石含量降低,钾型鸟粪石、 Ca₃(PO₄)₂·xH₂O含量呈逐渐增加趋势;pH由10.0升至12.0时,鸟粪石含量急剧下降,Ca₃(PO₄)₂·xH₂O和Mg(OH)₂含量快速增加,而钾型鸟粪石快速增加并在pH 11.0达到最大后急剧下降.因此,回收养猪废水中的磷时要获得纯度高的鸟粪石产品,pH值应控制在8.0～9.0.     

废水中鸟粪石回收的机器学习预测和优化

基于机器学习的方法，探究了从模拟废水中以鸟粪石的形式回收氮和磷的问题。利用极限梯度提升算法(XGBoost)和随机森林(RF)模型对磷回收率和氮回收率进行单目标和多目标预测，明确了7种工艺条件对鸟粪石结晶的影响。XGBoost在单目标(R²=0.91～0.93)和多目标(R²=0.89)的预测方面表现均优于RF。此外，在P初始浓度为10 mg/L和1 000 mg/L的情况下，通过实验验证了多目标模型的优化解集，得到鸟粪石回收的最佳工艺条件为N∶P比值为1.2∶1,Mg∶P为1∶1,pH为9.5,反应时间为80 min,反应温度为25℃,搅拌速率为240 r/min。     

超滤-反渗透集成膜技术深度处理酒精废水

采用超滤-反渗透集成膜技术对酒精废水二级生化处理出水进行深度处理,考察了不同超滤膜对废水的预处理性能,研究了超滤-反渗透集成膜技术对废水污染物的去除效果,并探索了不同清洗方式对反渗透膜通量恢复的影响。试验结果表明:超滤能有效地去除废水浊度和大分子有机物,为反渗透提供良好的进水水质;超滤-反渗透膜系统产水浊度、硬度、总铁均小于0.1 NTU、0.03 mmol/L和0.03 mg/L,电导率处于60~120μS/cm之间,可回用作锅炉补充水;酸洗+碱洗组合清洗方式能有效恢复反渗透膜通量,其废水膜通量可恢复为新膜废水通量的93.75%。     

Phosphorus recovery from wastewater by struvite crystallization：Property of aggregates

Struvite crystallization is a promising method to remove and recover phosphorus from wastewater to ease both the scarcity of phosphorus rock resources and water eutrophication worldwide. To date, although various kinds of reactor systems have been developed, supporting methods are required to control the struvite fines flushing out of the reactors. As an intrinsic property, aggregation is normally disregarded in the struvite crystallization process, although it is the key factor in final particle size and therefore guarantees phosphorus recovery efficiency. The present study developed a method to analyze the characteristics of struvite aggregates using fractal geometry, and the influence of operational parameters on struvite aggregation was evaluated. Due to its typical orthorhombic molecular structure, struvite particles are prone to crystallize into needle or rod shapes, and aggregate at the corners or edges of crystals. The determined fractal dimension(Dpf) of struvite aggregates was 1.52–1.31, with the corresponding range of equivalent diameter(d0.5) at 295.9–85.4 μm. Aggregates formed in relatively low phosphorus concentrations(3.0–5.0 mmol/L) and mildly alkaline conditions(pH 9.0–9.5) displayed relatively compact structures, large aggregate sizes and high aggregation strength. Increasing pH values led to continuous decrease of aggregate sizes, while the variation of Dpfwas insignificant. As to the aggregate evolution, fast growth in a short time followed by a long steady stage was observed.     

Fouling distribution in forward osmosis membrane process

Fouling behavior along the length of membrane module was systematically investigated by performing simple modeling and lab-scale experiments of forward osmosis （FO） membrane process. The flux distribution model developed in this study showed a good agreement with experimental results, validating the robustness of the model. This model demonstrated, as expected, that the permeate flux decreased along the membrane channel due to decreasing osmotic pressure differential across the FO membrane. A series of fouling experiments were conducted under the draw and feed solutions at various recoveries simulated by the model. The simulated fouling experiments revealed that higher organic （alginate） fouling and thus more flux decline were observed at the last section of a membrane channel, as foulants in feed solution became more concentrated. Furthermore, the water flux in FO process declined more severely as the recovery increased due to more foulants transported to membrane surface with elevated solute concentrations at higher recovery, which created favorable solution environments for organic adsorption. The fouling reversibility also decreased at the last section of the membrane channel, suggesting that fouling distribution on FO membrane along the module should be carefully examined to improve overall cleaning efficiency. Lastly, it was found that such fouling distribution observed with co-current flow operation became less pronounced in counter- current flow operation of FO membrane process.     

硫磺/石灰石自养反硝化系统脱氮除磷性能研究

为了考察硫磺/石灰石系统对于低C/N的城市污水进行同步脱氮除磷的性能,设计了体积比为1∶1的硫磺/石灰石柱式反应器,以人工配水为处理对象,采用厌氧生物滤池运行方式,研究了HRT、初始磷浓度、pH、温度等因素对其脱氮除磷性能的影响.结果表明,在进水NO 3^--N为30 mg/L左右,PO4^3--P为15 mg/L条件...     

连续微滤用于钢铁厂废水处理的生产性测试

采用国产连续微滤膜(CFM)系统对多源进水条件下钢铁污水处理厂生物处理出水进行深度处理,通过现场实测其进出水水质和性能参数,分析了该系统对钢铁废水生化二级出水的水质处理效果及其运行状况,结果表明:连续微滤膜(CFM)系统运行稳定,具有较强的耐污能力,对水中COD平均去除率约为19.6%,SS平均去除率约为72.7%,总氮和总磷的去除率随进水水质变化波动较大,通过该系统膜的截留作用可有效去除水中COD、悬浮物、胶体和有机颗粒,能够使水质满足多用途回用和反渗透预处理要求。河流划分为容量型、点源污染型、农业面源型和混合型等四种类型。建议对不同类型河流应采取不同控制对策,点面结合,综合防治。系统每3～5周左右进行化学反洗后,膜通量与跨膜压差等膜性能参数可基本恢复至起始水平。     

Fatty acid fouling of forward osmosis membrane: Effects of pH, calcium, membrane orientation, initial permeate flux and foulant composition

Octanoic acid (OA) was selected to represent fatty acids in effluent organic matter (EOM). The effects of feed solution (FS) properties, membrane orientation and initial permeate flux on OA fouling in forward osmosis (FO) were investigated. The undissociated OA formed a cake layer quickly and caused the water flux to decline significantly in the initial 0.5 hr at unadjusted pH 3.56; while the fully dissociated OA behaved as an anionic surfactant and promoted the water permeation at an elevated pH of 9.00. Moreover, except at the initial stage, the sudden decline of water flux (meaning the occurrence of severe membrane fouling) occurred in two conditions: 1. 0.5 mmol/L Ca^2 +, active layer facing draw solution (AL-DS) and 1.5 mol/L NaCl (DS); 2. No Ca^2 +, active layer-facing FS (AL-FS) and 4 mol/L NaCl (DS). This demonstrated that cake layer compaction or pore blocking occurred only when enough foulants were absorbed into the membrane surface, and the water permeation was high enough to compact the deposit inside the porous substrate. Furthermore, bovine serum albumin (BSA) was selected as a co-foulant. The water flux of both co-foulants was between the fluxes obtained separately for the two foulants at pH 3.56, and larger than the two values at pH 9.00. This manifested that, at pH 3.56, BSA alleviated the effect of the cake layer caused by OA, and OA enhanced BSA fouling simultaneously; while at pH 9.00, the mutual effects of OA and BSA eased the membrane fouling.