Effect of humic substances on the precipitation of calcium phosphate

For phosphorus （P） recovery from wastewater, the effect of humic substances （HS） on the precipitation of calcium phosphate was studied. Batch experiments of calcium phosphate precipitation were undertaken with synthetic water that contained 20 mg/L phosphate （as P） and 20 mg/L HS （as dissolved organic carbon, DOC） at a constant pH value in the range of 8.0-10.0. The concentration variations of phosphate, calcium （Ca） and HS were measured in the precipitation process; the crystalline state and compositions of the precipitates were analysed by powder X-ray diffraction （XRD） and chemical methods, respectively. It showed that at solution pH 8.0, the precipitation rate and removal efficiency of phosphate were greatly reduced by HS, but at solution pH ≥9.0, the effect of HS was very small. The Ca consumption for the precipitation of phosphate increased when HS was added; HS was also removed from solution with the precipitation of calcium phosphate. At solution pH 8.0 and HS concentrations ≤3.5 mg/L, and at pH ≥ 9.0 and HS concentrations ≤ 10 mg/L, the final precipitates were proved to be hydroxyapatite （HAP） by XRD. The increases of solution pH value and initial Ca/P ratio helped reduce the influence of HS on the precipitation of phosphate.     

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...     

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。     

磷酸铵镁沉淀法处理制药废水试验研究

制药废水由于制药原料化学纯度较高,废水中常含高浓度氮、磷污染物,采用磷酸铵镁沉淀法可同时回收两种元素不仅可以有效同时去除两种污染物,而且可以得到附加值较高的磷酸铵镁盐,因此本研究用磷酸铵镁化学沉淀法小试实验处理制药废水,讨论了磷酸铵镁沉淀法pH、晶种、初始浓度对P0^3- 4和NI-14同时去除的影响。试验结果表明：投加镁盐,在pH=9．5的条件下,可去除90％PO^3- 4,同时可去除15％NH4,在Po^-3 4和NH4浓度较低时,投加晶种可使Po;一去除率提高20％,该法渴望为制药废水处理提供创造经济效益的经验。     

碳酸盐体系中pH对Cu2+诱导结晶过程的影响

在流化床中,以含Cu2+废水为处理对象,考察了碳酸盐体系中pH的改变对Cu2+诱导结晶过程的影响. 结果表明:当进水ρ(Cu2+)为200 mg/L、沉淀剂pH为10.2时,经回流系统拦截,微晶产率可降低0.5%~1.0%,Cu2+的去除率可达99.0%以上. 经XRD(X射线衍射)分析表明,结晶产物以碱式碳酸铜为主,晶型呈短杆状,尺寸较为均一;当沉淀剂pH升至12.2时,Cu2+的去除率降至95.0%,系统出水结晶产物晶型特征不明显,尺寸不均,XRD结果显示为氢氧化铜、碱式碳酸铜、碳酸钙等混合结晶产物,晶体衍射峰多存在宽化现象,表明高pH下结晶产物晶化程度较低.      

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.     

Water softening by induced crystallization in fluidized bed

Fluidized bed and induced crystallization technology were combined to design a new type of induced crystallization fluidized bed reactor. The added particulate matter served as crystal nucleus to induce crystallization so that the insoluble material, which was in a saturated state, could precipitate on its surface. In this study, by filling the fluidized bed with quartz sand and by adjusting water p H, precipitation of calcium carbonate was induced on the surface of quartz sand, and the removal of water hardness was achieved.With a reactor influent flow of 60 L/hr, a fixed-bed height of 0.5 m, pH value of 9.5, quartz sand nuclear diameter of 0.2–0.4 mm, and a reflux ratio of 60%, the effluent concentration of calcium hardness was reduced to 60 mg/L and 86.6% removal efficiency was achieved. The resulting effluent reached the quality standard set for circulating cooling water. Majority of the material on the surface of quartz sand was calculated to be calcium carbonate based on energy spectrum analysis and moisture content was around 15.994%. With the low moisture content, dewatering treatment is no longer required and this results to cost savings on total water treatment process.     

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。     

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.     

载镁天然沸石复合材料对污水中氮磷的同步回收

采用载镁天然沸石为沉淀剂,以鸟粪石的形式回收模拟污水中的营养物质,考察了投加量、溶液pH、反应时间和共存Ca~(2+)对回收过程的影响,并利用FTIR、XRD、BET和SEM等手段对回收沉淀产物进行了化学组分和表面形貌分析,以揭示其回收机制.结果表明当材料投加量为0.4 g·L~(-1),溶液初始pH为7,反应时间为2 h时,载镁天然沸石对溶液中磷酸盐和氨氮的回收性能最佳,最大吸附量分别高达119.2 mg·g~(-1)和48.5 mg·g~(-1).载镁天然沸石对溶液中磷酸盐和氨氮的回收过程均符合拟二级动力学模型(R~20.99).载镁天然沸石对污水中营养物质的回收机制有鸟粪石化学沉淀、物理吸附、离子交换和静电吸附等,其中以鸟粪石沉淀法为主.共存Ca~(2+)会干扰载镁沸石对溶液中氮磷的同步回收,导致回收的沉淀组分除鸟粪石晶体外,还会存在部分磷酸钙等副产物.     

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。     

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.     

Seed selections for crystallization of calcium phosphate for phosphorus recovery

Seed induces and promotes the crystallization of calcium phosphate, and acts as carrier of the recovered phosphorus （P）. In order to select suitable seed for P recovery from wastewater, three seeds including Apatite （AP）, Juraperle （JP） and phosphate-modified Juraperle （M-JP） were tested and compared. Batch and fixed-bed column experiments of seeded crystallization of calcium phosphate were undertaken by using synthetic wastewater with 10 mg/L P phosphate. It shows that AP has bad enduring property in the crystallization process, while JP has better performance for multiple uses, and M-JP is a hopeful seed for P recovery by crystallization of calcium phosphate.     

三种有机酸对磷酸钙法回收模拟养猪场污水中磷的影响

采用磷酸钙(Calcium Phosphate,CP)结晶法回收模拟养猪场污水中的磷,考察了不同pH值条件下,3种有机酸(柠檬酸、丁二酸和乙酸)对模拟污水中磷去除率的影响,并利用扫描电镜和X射线衍射仪对结晶产物进行了表征.结果表明,CP结晶反应的最佳pH值约为9.5.在相同pH值条件下,柠檬酸对CP结晶反应中磷的去除效率和速率均有显著影响,高浓度柠檬酸能够完全抑制CP结晶反应,导致磷的去除率小于5%.相比之下,丁二酸和乙酸对磷的去除效率和速率影响不明显.3种有机酸对CP结晶产物的形状没有明显影响,所得产物均呈不定形的块状,但产物体积大小会随有机酸浓度升高而明显减小.不同浓度丁二酸和乙酸存在条件下均能得到羟基磷酸钙(Hydroxylapatite,HAP)晶体,但柠檬酸的存在会影响所得产物晶形.     

沉淀-Fenton氧化预处理甲基硫菌灵废水

研究沉淀-Fenton氧化对甲基硫菌灵生产废水的预处理,考察SCN^-和CODcr的去除效果。先加入Cu-SO4和Na2S2O3对SCN^-进行沉淀,考察CuSO4和Na2S2O3加入量对CODcr去除率的影响;对沉淀后水样进行Fenton氧化,通过改变pH值、H2O2浓度、Fe^2＋浓度、反应时间等得出该农药废水在常温下的最佳操作条件。实验结果表明,经过沉淀处理后的废水,pH值为4、H2O2投加量为6～7 g/L、Fe^2＋投加量为1.2～1.5 g/L,氧化时间为2～4 h,CODcr浓度从12 000 mg/L降至3 600 mg/L,总去除率达到了70%。     

A pilot-scale study of cryolite precipitation from high fluoride-containing wastewater in a reaction-separation integrated reactor

Fluoride removal by traditional precipitation generates huge amounts of a water-rich sludge with low quality, which has no commercial or industrial value. The present study evaluated the feasibility of recovering fluoride as low water content cryolite from industrial fluoride-containing wastewater. A novel pilot-scale reaction-separation integrated reactor was designed. The results showed that the seed retention time in the reactor was prolonged to strengthen the induced crystallization process. The particle size of cryolite increased with increasing seed retention time, which decreased the water content. The recovery rate of cryolite was above 75% under an influent fluoride concentration of 3500 mg/L, a reaction temperature of 50℃, and an influent flow of 40 L/hr. The cryolite products that precipitated from the reactor were small in volume, large in particle size, low in water content, high in crystal purity, and recyclable.     

白云石石灰流化结晶污水除磷工艺

实验研究了白云石石灰流化床工艺除磷的可行性.石灰一方面可以提高水体的pH值并提供充足的Ca2+、Mg2+,另一方面可作为晶种加快结晶沉淀反应,提高磷去除效率,是一种廉价高效的药剂.设计了新型气体搅动式白云石石灰流化床结晶反应器,以模拟污水厂污泥厌氧消化上清液为处理对象,实验考察了药剂投加量、停留时间和曝气量对反应器运行的影响.结果表明:药剂投加量在600~650 mg·L-1、停留时间5.0 h及曝气量50 mL·min-1的条件下,可以获得较好的磷去除效果,去除率可达87.0%.采用扫描电子显微镜、X射线衍射和傅里叶变换红外光谱对产物进行了表征,发现磷主要以磷酸铵镁(MAP)和羟基磷灰石(HAP)两种形式去除;由于反应体系碱度较高,产物中混杂大量CaCO3.     

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.     

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...