【作者】 汤琪；

【导师】 罗固源；

【作者基本信息】 重庆大学 ， 环境工程， 2008， 博士

【摘要】 论文提出了在优化试验的基础上,用磷酸铵镁沉淀法处理高浓度氨氮废水和磷酸盐废水,使处理出水的TP含量在10mg/L左右,NH3-N含量在50mg/L左右,与生活污水的氮、磷含量接近,然后把处理出水与生活污水按一定比例混合,用SBR生物处理工艺处理混合污水使其达标排放。论文详细探讨了沉淀剂种类、废水pH值、物质摩尔配比、反应时间、反应温度、物质浓度、搅拌速度、沉淀剂的加入方式、陈化时间等因素对同时脱氮除磷效果的影响。探讨了磷酸铵镁沉淀法处理磷酸盐工业废水、垃圾渗滤液、磷酸盐工业废水和垃圾渗滤液综合废水。并探讨了用SBR法进一步处理磷酸铵镁法处理出水的可行性及其影响因素。对磷酸铵镁脱氮除磷技术的相关机理进行了研究。论文主要研究内容与结论如下:①试验表明,影响磷酸铵镁脱氮除磷的主要因素有:1)沉淀剂种类:处理高浓度氨氮废水的较佳沉淀剂为:Na2HPO4.12H2O+ MgCl2.6H2O和Na2HPO4.12H2O+ MgSO4.7H2O。处理高浓度磷酸盐废水的较佳沉淀剂为:NH4Cl+ MgCl2.6H2O和NH4Cl+ MgSO4.7H2O。处理同时含高浓度氨氮和磷酸盐废水的较佳沉淀剂为:MgCl2.6H2O和MgSO4.7H2O。2) pH值:pH=8.5¹0.0范围内有比较好的同时脱氮除磷效果,pH=9.5时同时脱氮除磷效果最好。3) Mg:P:N摩尔配比:废水的氨氮和磷酸盐含量不同,最佳的Mg:P:N摩尔配比也不同。处理PO₄^3--P含量为1700¹800mg/L的磷酸盐工业废水的最佳的Mg:P:N=1.4:1.11:1.0,处理NH3-N含量为2500²600mg/L的垃圾渗滤液的最佳的Mg:P:N=1.3:1.15:1.0,综合处理上述磷酸盐工业废水和垃圾渗滤液的最佳的Mg:P:N=1.5:1.187:1.0。4)陈化作用:陈化作用能明显影响氨氮和磷酸盐去除率,当生成的沉淀物质绝大部分是磷酸铵镁时,陈化时间在24h左右,处理出水中的氨氮残留量可降低10%左右,磷酸盐残留量可降低5%左右。5)搅拌速度:搅拌速度太低（如:50 r/min）或太高（如:500 r/min）时同时脱氮除磷效果较差,搅拌速度为200 r/min左右时的同时脱氮除磷效果最好。②使处理出水的TP在10mg/L左右,NH3-N含量在50 mg/L左右,磷酸铵镁沉淀法处理不同废水的较佳试验条件为:1)处理PO₄^3--P含量为1700¹800 mg/L的磷酸盐工业废水时,搅拌速度为200 r/min左右,反应时间为20 min,pH=9.5,Mg:P:N=1.4:1.11:1.0。在陈化时间为30min以及在上述试验条件下,PO₄^3--P的去除率为98.69%,处理出水的PO₄^3--P含量为9.16 mg/L,NH3-N含量为64.10mg/L。2)处理NH3-N含量为2500²600mg/L的垃圾渗滤液时,搅拌速度为200 r/min左右,反应时间为20 min,pH=9.5, Mg:P:N=1.3: 1.15:1.0。在陈化时间为30min以及在上述试验条件下,NH3-N的去除率为97.05%,处理出水NH3-N含量为75.86 mg/L,PO₄^3--P含量为8.35mg/L。3)综合处理NH3-N含量为2500²600mg/L的垃圾渗滤液和PO₄^3--P含量为1700¹800 mg/L的磷酸盐工业废水时,搅拌速度为200 r/min左右,反应时间为20 min,pH=9.5,Mg:P:N=1.5:1.187:1.0。在陈化时间为30min以及在上述试验条件下,PO₄^3--P去除率为99.53%,NH3-N去除率为87.56%,处理出水的PO₄^3--P含量为6.79 mg/L,NH3-N含量为76.12 mg/L。通过X-衍射光谱和扫描电镜表征,处理几种废水所得到的沉淀物绝大部分是磷酸铵镁。③试验表明,常规的活性污泥经过逐步提高含盐量的驯化,在废水的电导率为15000μs/cm左右时,活性污泥仍有很好的COD去除效果和脱氮除磷效果。磷酸铵镁沉淀法处理出水用SBR法进行处理的较佳试验运行工况为:1)磷酸盐工业废水处理出水和生活污水按体积比约为1:1的比例混合,混合污水的电导率约为15000μs/cm,COD约为320.0mg/L,TN约为50mg/L,TP约为7.0mg/L。运行周期为10h（其中厌氧1.5h,好氧4.5h,缺氧2.5h,后耗氧0.5h,沉淀排水和闲置1.0h）。出水TN小于15mg/L、TP小于1.0mg/L、COD约为22mg/L,TN、TP、COD去除率可达到75%、86%、92%左右。2)垃圾渗滤液处理出水和生活污水按体积比约为1:4的比例混合,混合污水的电导率约为15000μs/cm,COD约为1150.0mg/L, TN约为48mg/L,TP约为6.0mg/L。运行周期为12h（其中厌氧2.0h,好氧5.0h,缺氧3.5h,后耗氧0.5h,沉淀排水和闲置1.0h）。出水TN小于15 mg/L、TP小于1.0mg/L、COD约为110mg/L,TN、TP、COD去除率可达到77%、87%、90%左右。3)磷酸盐工业废水和垃圾渗滤液综合废水的处理出水和生活污水按体积比约为1:1的比例混合,混合污水的电导率约为15000μs/cm, COD约为630.0mg/L,TN约为51mg/L,TP约为6.0mg/L。运行周期为10h（其中厌氧1.5h,好氧4.5h,缺氧2.5h,后耗氧0.5h,沉淀排水和闲置1.0h）。出水TN小于15 mg/L、TP小于1.0mg/L、COD约为45mg/L,TN、TP、COD去除率可达到78%、88%、93%左右。④动力学试验的研究表明,在pH=9.5时,体系主要发生的总反应为: Mg2++NH4++HPO42-+6H2O→MgNH4PO4·6H2O↓+H+该反应为二级反应,平衡常数为Kθ=1.92,速率常数为k=3.75L.mol^-1.s^-1,活化能Ea = 14. 02KJ.mol^-1。用SBR法处理磷酸盐工业废水和垃圾渗滤液综合处理出水和生活污水的混合污水时,厌氧段COD去除动力学方程为: C t = C0 e^-0.1888Xt;厌氧段的释磷动力学方程为: C_Pt= CP0 +0 .0459C0(1-e^-0.1888Xt);好氧段COD的去除动力学方程为: Ct = C0 e^-0.0963Xt;好氧段吸磷动力学方程为: C_pt = Cp0 e^-0.1671Xt ;缺氧段的反硝化吸磷动力学方程为: C_pt = Cp0 e^-0.0773Xt。更多还原

【Abstract】 The dissertation put forward that the high ammonia-nitrogen and phosphate wastewater is treated by magnesium ammonium phosphate （MAP） process.The concentration of TP is about 10 mg/L, the concentration of NH3-N is about 50 mg/L in the treated water. The treated water can be more treated along with domestic sewage by SBR. Some factors affecting the result of removal of ammonium and phosphate by MAP process are discussed, such as precipitator, pH, molar ratio, reaction time, reaction temperature,concentration,stirring speed,precipitation time,addition style of precipitator. Phosphate wastewater, landfill leachate, colligate wastewater of phosphate wastewater and landfill leachate are treated by MAP. The feasibility and affecting factors that the treated water is more treated by SBR are discussed. Some mechanism of the technology of MAP are studied.This research was mainly carried out in the following several aspects:①The experimental results show that, the mainly affecting factors of technology of MAP is as follows:1) Precipitation reagent :When high ammonia-nitrogen sweage is treated, better precipitation reagent is Na2HPO4.12H2O+MgCl2.6H2O and Na2HPO4.12H2O+ MgSO4.7H2O. When high phosphate sweage is treated, better precipitation reagent is NH4Cl+MgCl2.6H2O and NH4Cl+MgSO4.7H2O. When high ammonia-nitrogen and phosphate sweage is treated, better precipitation reagent is MgCl2.6H2O and MgSO4.7H2O.2) pH: On condition that pH is 8.5 to 10.0, the result of removal of ammonium and phosphate is good. On condition that pH is 9.5, the result of removal of ammonium and phosphate is best.3) Mg:P:N: If the concentration of NH3-N and PO₄^3--P is different, the best Mg: P: N is different. When treating the phosphate wastewater that the concentration of PO₄^3--P is 1700¹800 mg/L, the best Mg: P:N is 1.4:1.11:1.0. When treating the landfill leachate that the concentration of NH3-N is 2500²600mg/L, the best Mg:P:N is Mg:P: N=1.3:1.15:1.0. When treating above landfill leachate and phosphate wastewater, the best Mg:P:N is Mg:P:N=1.5: 1.187:1.0.4) Precipitation action: Precipitation action can affect the removal rate of ammonium and phosphate evidently. On condition that precipitation time is 24h,the concentration of NH3-N can be decreased by 10 percent and the concentration of PO₄^3--P can be decreased by 5 percent in the treated water.5) Stirring speed: On condition that stirring speed is too low（50 r/min） or too high（500r/min）,the result of removal of ammonium and phosphate is bad. On condition that stirring speed is about 200 r/min,the result of removal of ammonium and phosphate is best.②On condition that the concentration of TP is about 10 mg/L, the concentration of NH3-N is about 50 mg/L in the treated water,the better experimental condition of wastewater treated by MAP process is as follows:1) When treating the phosphate wastewater that the concentration of PO₄^3--P is 1700¹800 mg/L, stirring speed is about 200 r/min, reaction time is 20min, pH=9.5, Mg:P:N =1.4:1.11:1.0.When on these treatment condition and precipitation time is 30min ,the removal ratio of PO₄^3--P is 98.69%.The concentration of PO₄^3--P in the treated water is 9.16 mg/L. The concentration of NH3-N in the treated water is 64.10 mg/L.2) When treating the landfill leachate that the concentration of NH3-N is 2500²600mg/L, stirring speed is about 200 r/min, reaction time is 20min, pH=9.5, Mg:P:N =1.3:1.15:1.0. When on these treatment condition and precipitation time is 30min ,the removal ratio of NH3-N is 97.05%.The concentration of NH3-N in the treated water is 75.86mg/L. The concentration of PO₄^3- -P in the treated water is 8.35mg/L.3) When treating the landfill leachate that the concentration of NH3-N is 2500²600mg/L and the phosphate wastewater that the concentration of PO₄^3--P is 1700¹800 mg/L, stirring speed is about 200 r/min, reaction time is 20min,pH=9.5, Mg:P:N=1.5:1.187:1.0. When on these treatment condition and precipitation time is 30min ,the removal ratio of PO₄^3--P is 99.53%.The concentration of PO₄^3--P in the treated water is 6.79 mg/L, the removal ratio of NH3-N is 87.56%.The concentration of NH3-N in the treated water is 76.12 mg/L. MAP is confirmed by the scanning microscopy（SEM） and energy dispersive X-ray spectroscopy（EDS）.③The experimental results show that Common sludge has good activity in wastewater that conductivity is about 15000μs/cm ,on condition that common sludge is domesticated by increasing salt quantity little by little. The better operating conditions of treated water by SBR process is as follows:1) The treated water of phosphate wastewater and domestic sewage are mixed by 1:1.The conductivity is about 15000μs/cm, the concentration of COD is about 320.0mg/L, the concentration of TN is about 50 mg/L, the concentration of TP is about 7.0mg/L in the mix sewage. Operating period is 10h（anaerobic time is 1.5h, aerobic time is 4.5h, anoxic time is 2.5h, next aerobic time is 0.5h, drain and leave unused time is 1.0h）.The removal ratio of TN, TP, COD is about 75%, 86%, 92%. The concentration of TN is less than 15 mg/L, the concentration of TP is less than 1.0 mg/L, the concentration of COD is about 50mg/L in influent.2) The treated water of landfill leachate and domestic sewage are mixed by 1:4. The conductivity is about 15000μs/cm, the concentration of COD is about 1150.0mg/L, the concentration of TN is about 48 mg/L, the concentration of TP is about 6.0mg/L in the mix sewage. Operating period is 12h（anaerobic time is 2.0h, aerobic time is 5.0h, anoxic time is 3.5h, next aerobic time is 0.5h,drain and leave unused time is 1.0h ）.The removal ratio of TN, TP, COD is about 77%, 87%, 90%. The concentration of TN is less than 15 mg/L, the concentration of TP is less than 1.0 mg/L, the concentration of COD is about 110mg/L in influent.3) The treated water of colligate wastewater of phosphate wastewater and landfill leachate and domestic sewage are mixed by 1:1. The conductivity is about 15000μs/cm , the concentration of COD is about 630.0mg/L, the concentration of TN is about 51 mg/L, the concentration of TP is about 6.0mg/L in the mix sewage. Operating period is 10h（anaerobic time is 1.5h, aerobic time is 4.5h, anoxic time is 2.5h, next aerobic time is 0.5h, drain and leave unused time is 1.0h ）.The removal ratio of TN, TP, COD is about 78%, 88%, 93%. The concentration of TN is less than 15 mg/L, the concentration of TP is less than 1.0 mg/L, the concentration of COD is about 45mg/L in influent.④The kinetic experimental results show that the overall reaction of MAP system is as fllows:Mg2++NH4++HPO42-+6H2O→MgNH4PO4·6H2O↓+H+.The balance constant of above reaction is 1.92.This reaction is 2nd order reaction. The rate constants of above reaction is 3.75L.mol^-1.s^-1. The activation energy is 14 .02KJ .mol^-1.The treated water of colligate wastewater of phosphate wastewater and landfill leachate and domestic sewage are mixed by 1:1. The kinetic equation of mix sewage by SBR process is as follows: The kinetic equation of COD removal is XtC t = C0 e-0.1888 in anaerobic period. The kinetic equation of releasing phosphor is C_Pt= CP0 +0 .0459C0（1-e-0.1888Xt） in anaerobic period. The kinetic equation of COD removal is Ct = C0 e-0.0963Xt in aerobic period. The kinetic equation of absorbing phosphor is C_pt = Cp0 e-0.1671Xtin aerobic period.The kinetic equation of denitrifying dephosphatation is C_pt = Cp0 e-0.0773Xtin anoxic period.更多还原