利用浊度分析法研究硅酸对磷酸钙沉淀的影响

磷酸钙沉淀法是从污水中回收磷的最常用的方法之一.本文通过测定溶液浊度的方法研究了钙磷比为2∶1的条件下pH和硅酸对磷酸钙沉淀的影响.结果发现,pH低于6时,短时间内溶液中不能形成磷酸钙沉淀;而pH大于7时,溶液中迅速生成磷酸钙沉淀,且随pH的增加沉淀速度变大.XRD谱图表明,pH=7或8时都生成热力学最稳定的羟基磷酸钙沉淀.7 mg·L-1单硅酸的存在使生成的磷酸钙溶液的初始浊度从10NTU增加到20 NTU,使磷酸钙沉淀速度加倍,说明单硅酸能促进磷酸钙的沉淀速度.而聚硅酸使溶液初始浊度从10 NTU降低到0 NTU,抑制了磷酸钙的沉淀速度,表明不同形态的硅酸对磷酸钙的沉淀速度有不同的影响.XRD谱图表明,硅酸存在时,溶液中除了生成羟基磷酸钙外,还生成其他类型的磷酸钙.     

磷酸钙沉淀法同步去除污泥水中磷和腐殖质的优化研究

以含有腐殖质(HS)的含磷污水为处理对象,开展了磷酸钙结晶同步去除磷和HS的优化研究.通过响应面法考察了HS浓度、p H和Ca/P摩尔比(Ca/P)对正磷和HS去除效果的单独和联合效应,利用X射线衍射表征固体产物.结果表明,磷酸钙结晶法可同步去除磷和HS,HS的存在降低了除磷效率.p H对磷去除率有显著性影响,而Ca/P和HS浓度对HS去除率有显著性影响.三因素联合效应中Ca/P和HS浓度联合效应对HS去除率有显著性影响.提高反应p H有助于减小HS对磷酸钙除磷的影响,固体产物结晶度增强,但固体纯度降低.     

MAP 结晶法回收和去除尿液中的磷

以分解后的尿液为研究对象,采用MgCl₂·6H₂Ｏ 溶液作为MAP结晶剂,对MAP结晶同步回收尿液中的磷和部分氮的影响因素Mg/PO^３－₄-P摩尔比、反应pH、反应时间、沉淀时间和搅拌速度等进行小试试验.结果表明,Mg/PO^３－₄-P摩尔比是重要的运行参数,当其摩尔比超过1.3∶1时,磷的回收率超过95%,上清液剩余PO^３－₄-P浓度小于10 mg/Ｌ,而提高反应pH不能明显增加磷的回收率.该工艺的最佳运行条件为反应时间20 min,沉淀时间2.0 h,搅拌速度120 r/min,不需要pH调节控制.选择Mg/PO^３－₄-P摩尔比分别为1∶1、1.3∶1和1.5∶1,对在最佳条件下反应获得的3种产物采用SEM、XRD和ICP分析表明,3种产物都为比较纯净的MAP产品,其主要元素P、N、Mg的含量接近于MAP的理论含量（P=12.62%, N = 5.71%, Mg= 9.91%）,分别为13.54%, 5.34%,9.01% (Mg/PO^３－₄-P =1∶1)、13.78%,5.23%,9.36% (Mg/PO^３－₄-P =1.3∶1)和13.34%,5.12%,9.15% (Mg/PO^３－₄-P=1.5∶1),具有较高的回收利用价值.     

Phosphate removal and recovery through crystallization of hydroxyapatite using xonotlite as seed crystal

Xonotlite was synthesized and tested for phosphate removal and recovery from synthetic solution in a batch mode. The e ects of pH, initial calcium concentration, bicarbonate concentration on phosphate removal through crystallization were examined. The morphology and X-ray di raction (XRD) pattern of xonotlite before and after crystallization confirmed the formation of crystalline hydroxyapatite. The results indicated that the crystallization product had a very high P content (> 10%), which is comparable to phosphate rock at the dosage of 50–200 mg xonotlite per liter, with a maximum P content of 16.7%. The kinetics of phosphate removal followed the second-order reaction equation. The phosphate removal ability increased with increasing pH. The precipitation of calcium phosphate took place when pH was higher than 7.2, whereas the crystallization occurred at pH 6.0. A high calcium concentration could promote the removal of phosphate via crystallization, while a high bicarbonate concentration also enhanced phosphate removal, through that the pH was increased and thus induced the precipitation process. When xonotlite was used to remove phosphate from wastewater, the removal e ciency could reach 91.3% after 24 h reaction, with removal capacity 137 mg/g. The results indicated that xonotlite might be used as an e ective crystal seed for the removal and recovery of phosphate from aqueous solution.     

环境因素对菹草根和叶细胞质膜Ca2+-ATPase活性的影响

通过改变溶液温度、pH值、ATP浓度、钙浓度和培养液的钙浓度等条件,研究了菹草根和叶细胞质膜Ca2+-ATPase的活性的变化.结果表明,根细胞质膜Ca2+-ATPase的活性在pH 6.0时最高,其最适反应温度为40℃;叶细胞质膜Ca2+-ATPase在一个较宽的pH范围内具有高活性,最适反应温度为45℃;溶液中ATP浓度分别为3mmol/L和4mmol/L时菹草根和叶细胞质膜Ca2+-ATPase活性最大;无论是菹草根还是叶细胞质膜Ca2+-ATPase活性,在溶液钙浓度为10-4mol/L时都最高.在营养液中添加不同CaCl2浓度培养菹草,其根和叶细胞质膜Ca2+-ATPase活性表现出差异,根细胞质膜Ca2+-ATPase活性比叶细胞质膜Ca2+-ATPase活性高,且随营养液中钙浓度的增加,这种差异加大;当营养液中钙浓度在10mg/L(2.5×10-4 mol/L)以下时,Ca2+-ATPase活性逐渐上升,营养液中钙浓度由10mg/L增加到15mg/L,Ca2+-ATPase活性陡然下降,这与溶液钙浓度对Ca2+-ATPase活性的影响相呼应.     

化学镀镍老化液中镍、磷的处理与回收

以 Ca(OH) 2 作为沉淀剂 ,调节溶液 p H =1 2 ,在 80℃条件下反应 1 h,使化学镀镍老化液中镍浓度降到1 / mg· L- 1 ;分离沉淀后的溶液用硫酸调节 p H=8,按 Ca(Cl O) 2 与总 P重量比为 3 .5∶ 1 .0的比例加入 Ca(Cl O) 2 ,老化液中的磷酸盐通过形成沉淀得到去除 ,从而使化学镀镍老化液中的镍、磷含量均达到国家排放标准。对于含 Ni(OH) 2 的沉淀 ,以稀硫酸溶解回收其中的镍 ,剩余沉渣建议填埋处理 ;磷酸盐沉淀可以作为磷肥资源回用于农业生产。     

三峡库区香溪河流域磷矿废石磷素释放特性研究

以三峡库区香溪河流域内所堆存的磷矿开采废石为研究对象,分别利用去离子水和人工配制的酸雨(pH=4.5)作为淋溶液,采用动态柱淋溶的试验方法,对比分析了磷矿废石在中性和酸性淋溶条件下的磷素释放特性.结果表明,在中性淋溶条件下,磷矿废石淋出液将长期处于弱碱性状态(pH=7.0~9.0),而在酸性淋溶条件下,淋出液pH值将在液固比(L/S)达到0.5mL/g后由弱碱性(pH=8.0~9.0)转变为弱酸性(pH=6.0~7.0);磷矿废石淋出液中的总磷(TP)浓度主要受淋溶环境pH值的影响,呈现出随液相pH减小而增大的趋势,而淋溶时间的增加不会对淋出液中的TP浓度形成稀释效应;当淋溶环境的pH值相对稳定时,磷矿废石将以稳定的溶解速率向液相中释放磷素;而当淋溶环境的pH值由弱碱性向酸性转变时将形成磷素加速释放期;无论是在自然淋溶条件还是在酸性淋溶条件下,磷矿废石淋出液中的TP浓度均超出超过GB 8978-1996中所规定的III类水域TP的排放限值(0.5mg/L),应将其视为II类工业固体废弃物进行相应的处置,以降低其对香溪河库湾的磷污染风险.     

镁离子对氧化亚铁硫杆菌生物合成次生铁矿物的影响

通过摇瓶实验,在Mg2+分别为48,4.8mg/L,其他元素组成与9K液体培养基一致的体系中,采用氧化亚铁硫杆菌A. ferrooxidans催化合成次生铁矿物.考察了Mg2+含量对生物合成次生铁矿物体系pH值、氧化还原电位(ORP)、Fe2+氧化率、总Fe沉淀率、次生铁矿物矿相及矿物晶体尺寸的影响.结果表明,经过48h培养,Mg2+浓度为48,4.8mg/L生物成矿体系pH值分别从原来的2.50降低至2.30,2.19,ORP分别从初始259mV增加至269mV,276mV.两体系Fe2+氧化率培养至第48h均达到100%,然而两体系总Fe沉淀率及矿物形态及却不尽相同.Mg2+浓度为48mg/L生物成矿体系,总Fe沉淀率为23.7%,次生矿物紧密粘附于三角瓶底部.而Mg2+浓度为4.8mg/L生物成矿体系,总Fe沉淀率达到32.2%,次生矿物却均匀分散于溶液中.两体系合成次生铁矿物均为黄铁矾与施氏矿物共存的混合物,Mg2+含量4.8mg/L体系合成黄铁矾单个晶体长度(~1.60μm)约为Mg2+含量48mg/L体系的1.2倍.     

化学沉淀法回收污泥中氮磷的影响因素研究

污水处理厂污泥上清液中富集着较高浓度溶解性的氮磷,将此部分氮磷形成磷酸盐沉淀(如磷酸氨镁、磷酸钙、磷酸铝等)加以回收利用,受到各种因素的影响.文章以正交试验得出的影响因素为基础,深入研究了pH、初始PO43--p的浓度、Mg/P和反应时间对某污水厂污泥上清液中磷酸氨镁沉淀法回收氮磷的影响.结果表明:pH是影响污泥上清液...     

Characteristics of anoxic phosphors removal in sequence batch reactor

The characteristics of anaerobic phosphorus release and anoxic phosphorus uptake were investigated in sequencing batch reactors using denitrifying phosphorus removing bacteria （DPB） sludge. The lab-scale experiments were accomplished under conditions of various nitrite concentrations （5.5, 9.5, and 15 mg/L） and mixed liquor suspended solids （MLSS） （1844, 3231, and 6730 mg/L）. The results obtained confirmed that nitrite, MLSS, and pH were key factors, which had a significant impact on anaerobic phosphorus release and anoxic phosphorus uptake in the biological phosphorous removal process. The nitrites were able to successfully act as electron acceptors for phosphorous uptake at a limited concentration between 5.5 and 9.5 mg/L. The denitrification and dephosphorous were inhibited when the nitrite concentration reached 15 mg/L. This observation indicated that the nitrite would not inhibit phosphorus uptake before it exceeded a threshold concentration. It was assumed that an increase of MLSS concentration from 1844 mg/L to 6730 mg/L led to the increase of denitrification and anoxic P-uptake rate. On the contrary, the average P-uptake/N denitrifying reduced from 2.10 to 1.57 mg PO4^3--P/mg NO3^--N. Therefore, it could be concluded that increasing MLSS of the DEPHANOX system might shorten the reaction time of phosphorus release and anoxic phosphorus uptake. However, excessive MLSS might reduce the specific denitrifying rate. Meanwhile, a rapid pH increase occurred at the beginning of the anoxic conditions as a result of denitrification and anoxic phosphate uptake. Anaerobic P release rate increased with an increase in pH. Moreover, when pH exceeded a relatively high value of 8.0, the dissolved P concentration decreased in the liquid phase, because of chemical precipitation. This observation suggested that pH should be strictly controlled below 8.0 to avoid chemical precipitation if the biological denitrifying phosphorus removal capability is to be studied accurately.     

锌对磷酸铵镁和磷酸钙结晶回收磷的影响

以模拟废水为对象,研究了pH及Zn2+浓度对磷酸铵镁(MAP)和羟基磷灰石(HAP)法除磷率的影响,并对不同Zn:P摩尔比条件下除磷所得产物进行了XRD物相分析。结果表明,锌磷共存条件下进行MAP和HAP法除磷,当pH在7.4～8.0时,Zn2+浓度越大,除磷率越高,随着pH继续增加,Zn2+浓度越大,除磷率反而越小。当pH为9.5时,Zn2+浓度从0增加到25mg/L时,MAP法的除磷率从91%下降到82%;而HAP法的除磷率从95%下降到92%,受Zn2+浓度影响较MAP法小。锌磷共存条件下的除磷产物中均含有Zn(3PO4)2,随着溶液中Zn:P增加,产物中Zn(3PO4)2含量越来越多,且HAP法除磷产物纯度受Zn2+浓度影响较MAP法大。     

不同沉淀pH值条件下制备的水合氧化锆对水中磷酸盐的吸附作用

研究了沉淀pH值分别为4.8、8.0和10.6条件下制备的水合氧化锆对水中磷酸盐的吸附作用,结果表明,共存的Na~+仅仅略微促进了沉淀pH值为4.8和8.0时所得水合氧化锆对水中磷酸盐的吸附,却明显促进了沉淀pH值为10.6时所得水合氧化锆对磷酸盐的吸附.共存的Ca~(2+)仅仅略微促进了沉淀pH值为4.8时水合氧化锆对磷酸盐的吸附,却极大地促进了沉淀pH值为8.0和10.6时水合氧化锆对磷酸盐的吸附.共存的HCO_3~-和SO_4~(2-)抑制了水合氧化锆对磷酸盐的吸附,且它们对沉淀pH值为4.8时水合氧化锆吸磷的抑制作用明显大于对沉淀pH值为8.0和10.6时水合氧化锆的抑制作用.不同沉淀pH值条件下制备的水合氧化锆对水中磷酸盐的吸附能力均随着溶液pH值的增加而降低.不同沉淀pH值条件下所得水合氧化锆对水中磷酸盐的吸附平衡数据可以采用Langmuir、Freundlich和Dubinin-Redushckevich(D-R)等温吸附模型加以描述.存在Na+而不存在Ca~(2+)情况下,3种不同沉淀pH值条件下所得水合氧化锆对中性溶液中磷酸盐的最大单层吸附容量差别不大;存在Ca~(2+)情况下,沉淀pH值为8.0和10.6时所得水合氧化锆对中性溶液中磷酸盐的最大单层吸附容量远远高于沉淀pH值为4.8时制备的水合氧化锆.沉淀pH值为4.8和8.0时所得水合氧化锆的吸磷机制主要是表面氯和羟基基团与磷酸盐之间的配位体交换作用,而沉淀pH值为10.6时所得水合氧化锆的吸磷机制主要是表面羟基基团与磷酸盐之间的配位体交换作用.以上研究结果显示,与沉淀pH值为4.8时制备的水合氧化锆相比,沉淀pH值为8.0和10.6时制备的水合氧化锆更加适合作为吸附剂去除废水中的磷酸盐.     

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.     

Adsorption and recovery of phosphate from water by amine fiber, effects of co-existing ions and column filtration

A weak-base adsorption fiber, acrylic amine fiber (AAF), was prepared for removal and recovery of phosphate from water. The adsorption properties of the AAF for phosphate and effects of co-existing ions were investigated using batch and column filtration experiments, scanning electron microscope, and Fourier transform infrared techniques. Experimental results showed that AAF had a high phosphate adsorption capacity of 119?mg/g at pH?7.0. The effects of calcium, sulfate, carbonate, nitrate, and fluoride showed that sulfate and calcium inhibited phosphate adsorption. However, AAF showed higher binding affinity toward phosphate than sulfate. Column filtration results showed that AAF could filter 1420 bed volumes of tap water containing 1.0?mg-P/L of phosphate. The saturated AAF could be regenerated using 0.5?mol/L hydrochloric acid solution and reused. After desorption, phosphate was recovered through precipitation of hydroxyapatite (Ca₅(PO₄)₃OH). The easy of regeneration, good adsorption performance, and the fiber morphology of AAF make it an attractive alternative for phosphate recovery from multiple water sources.     

Removal of phosphate from wastewater using alkaline residue

Alkaline residue(AR) was found to be an efficient adsorbent for phosphate removal from wastewater. The kinetic and equilibrium of phosphate removal were investigated to evaluate the performance of modified alkaline residue. After treatment by NaOH(AR-NaOH), removal performance was significantly improved, while removal performance was almost completely lost after treatment by HCl(AR-HCl). The kinetics of the removal process by all adsorbents was well characterized by the pseudo second-order model. The Langmuir model exhibited the best correlation for AR-HCl, while AR was effectively described by Freundlich model. Both models were well fitted to AR-NaOH. The maximum adsorption capacities calculated from Langmuir equation were in following manner: AR-NaOH AR AR-HCl. Phosphate removal by alkaline residue was pH dependent process. Mechanisms for phosphate removal mainly involved adsorption and precipitation, varied with equilibrium pH of solution. For AR-HCl, the acid equilibrium pH( 6.0) was unfavorable for the formation of Ca-P precipitate, with adsorption as the key mechanism for phosphate removal. In contrast, for AR and ARNaOH, precipitation was the dominant mechanism for phosphate removal, due to the incrase on pH( 8.0) after phosphate removal. The results of both XRD and SEM analysis confirmed CaHPO4·2H2O formation after phosphate removal by AR and AR-NaOH.     

磷酸铵镁同时脱氮除磷技术研究

探讨了pH值,物质摩尔配比,反应时间,反应温度,物质浓度,陈化时间,沉淀剂加入方式等因素对MAP同时脱氮除磷效果的影响。确定了各影响因素的较佳值,并对各因素的影响机理进行了探讨。在兼顾处理液的含盐量尽量低,以及满足处理液中的磷含量<10mg/L,氨氮含量在20mg/L左右的条件下,优化出了处理氨氮浓度为0.1mol/L(1400mg/L)及磷酸盐为相应浓度的废水的最佳pH为9.5,最佳摩尔配比为n(Mg):n(P):n(N)=1.2:1.03:1.0。     

磷酸铵镁沉淀法预处理7-ACA综合废水试验研究

采用磷酸铵镁(MAP)沉淀法对高氨氮7-ACA综合废水进行了预处理试验研究,以Na2HPO4和MgCl2.6H2O作为沉淀剂,探讨了初始反应pH值、n(Mg2+):n(PO43-)/:n(NH4+)投配比及反应时间等因素对氨氮去除效果的影响。结合结晶物SEM分析,确定预处理的最佳工艺条件为:初始反应pH 9.0、n(Mg2+):n(PO43-):n(NH4+)投配比1.0:1.1:1和反应时间20 min。平行试验结果表明,在最佳工艺条件下,当进水氨氮浓度为1 020~1 190 mg/L时,处理后出水氨氮浓度为小于150.0 mg/L,氨氮去除率在85.0%以上,残磷量小于40.0 mg/L,为7-ACA综合废水的后续生化处理创造了有利条件。     

pH对以PBS为反硝化碳源和生物膜载体去除饮用水源水中硝酸盐的影响

PBS为一种新型可生物降解多聚物(BDPs),可以作为生物膜载体和碳源去除饮用水中的硝酸盐,对该工艺中pH的影响进行了研究.结果表明:PBS颗粒表面可以形成致密的生物膜,对膜内的反硝化菌形成良好的保护作用.PBS反硝化系统承受pH冲击负荷的能力优于传统填料为载体的反硝化系统,当进水pH介于5.0～9.0之间时,反硝化过程中溶液的pH趋向中性,硝态氮的去除速率为0.60～0.63 mg/(g·d),最高达到0.70 mg/(g·d)(pH 7.5～8.0).当溶液中pH在6～8之间时,出水亚硝酸盐不稳定;pH<6时,出水中亚硝酸盐浓度高达0.7 mg/L;pH>8时出水中的亚硝酸盐浓度低于0.1 mg/L.     

氢氧化钙清液加氯化钙处理酸性高浓度含氟废水

研究了pH值、氯化钙投加量、搅拌时间及沉淀时间等因素对酸性高浓度含氟废水处理效果的影响;提出了采用氢氧化钙清液加氯化钙作为新型沉淀剂处理酸性高浓度含氟废水的工艺参数：pH值在8．5－9．5,按照nCa／F=0．7加入5％CaCl2溶液,搅拌45min、沉降90min;采用此工艺参数处理氟离子浓度为2600mg／L、pH值为2．97的废水,能把废水氟离子的浓度降至20mg／L以下,达到国家二级排放标准;采用本工艺取代传统工艺的好处是：沉渣中氟化钙纯度高,有利于废水中氟的回收利用。     

Enhanced struvite recovery from wastewater using a novel cone-inserted fluidized bed reactor

The feasibility of struvite recovery at low （12.5 mg/L） and high （120 mg[L） phosphorus concentrations was studied by constructing a novel fluidized bed reactor with cones （FBRwc） and without cones （FBRwoc）. The crystallization process was continuously operated for 133 days under different hydraulic retention times （HRT = 1-10 hr）, pH （7.5-10）, and molar ratios of Mg/P （0.75-1.75）, N/P （1-10） and Ca/Mg （0-2）. The optimum operating conditions of HRT, pH, Mg/P and N/P molar ratios were found to be 2 hr, 9, 1.25, and 7.5, respectively. Under these optimum conditions, the phosphorus precipitation efficiencies of FBRwc were 93% for low and 98% for high phosphorus influent; however, the efficiencies were 78% and 81% for FBRwoc, respectively. Due to crystal losses at each junction （17%-31%）, the crystal recovery efficiency of FBRwoc was relatively low （47%-65%） for both influent concentrations. However, the losses were minimal in FBRwc, which showed 75% and 92% crystal recovery for low and high phosphorus concentrations, respectively. At low calcium concentration, crystal chemical analysis showed the product to be pure struvite （〉 99%）. The scanning electron microscope and X-ray diffraction results further confirmed that the crystal recovered from FBRwc contained pure struvite, which could be considered a high quality fertilizer. Except HRT, all parameters （pH, Mg/P, N/P and Ca/Mg） were found to be influencing factors for FBRwc performance. Overall, inserting cones in each part of the reactor played a significant role in enhancing struvite recovery from a wide range of phosphorus-containing wastewater.