The effects of magnesium and ammonium additions on phosphate recovery from greenhouse wastewater

Phosphorus recovery from greenhouse wastewater, using precipitation-crystallization, was conducted under three levels of calcium concentration, 304 mg/L (7.6 mmol/L), 384 mg/L (9.6 mmol/L), and 480 mg/L (12 mmol/L), and also with additions of ammonium and magnesium into the wastewater. Jar test results confirmed high phosphate removal, with more than 90% of the removal achieved with a pH as low as 7.7. Under the low calcium concentration, ammonium addition affected the chemical reactions at pH lower than 8.0, where struvite was produced; when the pH was raised to 8.8, other calcium compounds dominated the precipitation. Under the medium calcium concentration, ammonium and magnesium addition helped struvite precipitation in the low pH range. Hydroxyapatite (HAP) was the main product. Under the high calcium concentration, ammonium addition showed no effects on the precipitation.     

Overcoming challenges to struvite recovery from anaerobically digested dairy manure

Recovering struvite from dairy manure has consistently posed problems for researchers. This study separated solids from anaerobically digested dairy manure using a filtration system. Filtrate was rich in free magnesium (160 to 423 mg/L), ammonium (320 to 1800 mg N/L) and orthophosphate (93 to 332 mg P/L). High concentrations of free calcium (128 to 361 mg/L) and alkalinity (3309 to 6567 mg/L as CaCO3), however, may hinder struvite precipitation. Batch precipitation tests were conducted to identify and overcome factors that interfere with struvite formation. Precipitation tests at pH 9 identified calcium and ionic strength as most probable interferences. Calcium addition did not significantly change phosphorus removal efficiency, but decreased struvite purity because of formation of calcium phosphates when Ca:P activity ratio was greater than 0.5 to 1. Batch tests demonstrated effective calcium removal from anaerobically digested dairy manure through precipitation of calcium carbonate at pH 9 to 10 while retaining magnesium and orthophosphate, lessening hindrance to struvite formation.     

鸟粪石结晶法回收垃圾渗滤液氨氮研究

采用MgSO₄·7H₂O和Na₂HPO₄·12H₂O使NH₃-N生成MgNH₄PO₄·6H₂O（鸟粪石）结晶沉淀法回收渗滤液中NH₃-N。考察了pH值、反应时间、药剂配比对NH₃-N去除率的影响。结果表明，鸟粪石结晶回收NH₃-N反应的适宜pH值为9～9.5之间，过高的pH会破坏鸟粪石晶体结构，导致固定氨从MgNH₄PO₄中游离出来，不利于氨氮的去除。在pH值为9.5、反应时间为25 min、Mg²⁺∶NH⁺₄∶PO^3-₄=1.5∶1∶1.5的最佳条件下，渗滤液中NH₃-N浓度由初始3 500 mg/L,经结晶沉淀后降低至175 mg/L，去除率达95%。鸟粪石结晶沉淀过程中几乎不吸收重金属，同时回收了氨氮，其沉淀产物鸟粪石是一种优良的缓释肥原料。     

Coagulation and precipitation as post-treatment of anaerobically treated primary municipal wastewater.

The main objective of this study was to investigate the feasibility of coagulation as a post-treatment method of anaerobically treated primary municipal wastewater. Both mesophilic and ambient (20 degrees C) temperature conditions were investigated in a laboratory-scale upflow anaerobic sludge bed (UASB) reactor. In addition, optimization of the coagulant, both in terms of type and dose, was performed. Finally, phosphorus removal by means of aluminum and iron coagulation and phosphorus and ammonia nitrogen removal by means of struvite precipitation were studied. Anaerobic treatment of primary effluent at low hydraulic retention times (less than 15 hours) resulted in mean chemical oxygen demand (COD) removals ranging from 50 to 70%, while, based on the filtered treated effluent, the mean removals increased to 65 to 80%. Alum coagulation of the UASB effluent gave suspended solids removals ranging from approximately 35 to 65%. Turbidity removal reached up to 80%. Remaining COD values after coagulation and settling were below 100 mg/L, while remaining total organic carbon (TOC) levels were below 50 mg/L. Filterable COD levels were generally below 60 mg/L, while filterable TOC levels were below 40 mg/L. All coagulants tested, including prepolymerized aluminum and iron coagulants, demonstrated similar efficiency compared with alum for the removal of suspended solids, COD, and TOC. Regarding struvite precipitation, optimal conditions for phosphorus and nitrogen removal were pH 10 and molar ratio of magnesium: ammonia-nitrogen: phosphate-phosphorus close to the stoichiometric ratio (1:1:1). During struvite precipitation, removal of suspended solids reached 40%, while turbidity removal reached values up to 80%. The removal of COD was approximately 30 to 35%; yet, when removal of organic matter was based on the treated filterable COD, the removal increased to approximately 65%. In addition, nitrogen was removed by approximately 70%, while phosphorus removal ranged between approximately 30 and 45% on the basis of the initial phosphorus concentration. Finally, size fractionation of the organic matter (COD) showed that the various treatment methods were capable of removing different fractions of the organic matter.     

Phosphate Recovery from Greenhouse Wastewater

A study was conducted to investigate the suitability of phosphate recovery from greenhouse wastewaters by using precipitation/crystallization process. More than 90% of the phosphate could be removed from the greenhouse wastewater. Various calcium phosphate salts were obtained in the process; hydroxyapatite [Ca₅(PO₄)₃OH] could be the main product from the precipitates. Phosphate removal was affected by the presence of magnesium ion in wastewaters. An increase of magnesium concentrations in wastewaters decreased phosphate removal rates. The chemical contents of precipitates in terms of calcium, magnesium and phosphate were affected by calcium to magnesium molar ratio. Higher calcium contents were obtained at wastewaters with high calcium to magnesium molar ratio. An addition of magnesium did not affect the potassium contents in the precipitates. K‐struvite, MgKPO₄·6H₂O, was not the major product in the precipitate, even with addition of a large quantity of magnesium.     

苦土和氧化镁处理氮磷废水的对比研究

分别采用苦土、纯氧化镁为沉淀剂对模拟高浓度氮磷废水(N/P=0.8)进行了脱氮除磷研究,比较了沉淀剂投加量、pH对2种沉淀剂处理氮磷废水的影响,对沉淀产物进行XRD分析,并进行了经济效益比较。结果表明,pH是影响2种沉淀剂处理氮磷废水的主要因素,随着pH的增加,脱氮除磷效果提高,在平衡pH为9～10之间时氮磷处理效果最佳,pH继续增加,由于磷酸镁沉淀的形成使得氨氮去除率降低。此外,处理相同的废水,苦土的最佳投加量要大于纯氧化镁,但是经济效益比较结果表明,以苦土为沉淀剂处理氮磷废水可大大降低处理成本。     

鸟粪石法回收制肥工业废水中氨氮的中试研究

制肥工业废水中氨氮浓度高,难以直接进行生化反应,采用鸟粪石沉淀法可有效去除并回收氨氮。利用中试反应器回收某制肥工业废水中的氨氮,采用氯化镁与氧化镁作为联用镁源,通过考察不同进料方式、搅拌速度、停留时间等因素的影响,确定了鸟粪石法回收氨氮的最佳工况:采用间歇进水、固体投加镁源的投料方式,搅拌速度300 r/min,停留时间2 h。最佳条件下,氨氮去除率达到93.5%,磷残余率小于0.3%,生成的鸟粪石纯度可达85.6%,砷和铅的质量分数分别为0.0036和0.0008,符合肥料中重金属限值(GB/T 23349-2009),其他重金属均未检出。因此,回收产品有很好的利用价值。经济分析表明磷源是此方法处理成本较高的主要原因。     

神经节苷脂生产废水处理技术研究

针对神经节苷脂生产废水蛋白质含量高的特点，研究了等电点沉淀或混凝沉降预处理、厌氧好氧生物处理、化学沉淀和类Fenton氧化后处理组合工艺处理神经节苷脂生产废水的技术。结果表明，神经节苷脂生产废水的等电点在pH=2.2左右，通过等电点沉淀可去除30%以上的COD，但等电点时蛋白质的沉淀速度非常慢；用聚合硫酸铁对神经节苷脂生产废水进行混凝预处理的最适工艺条件是：pH=7～7.5，聚合硫酸铁用量＝500～750 mg/L。在优化条件下，混凝预处理可以使神经节苷脂生产废水的COD从27 000 mg/L左右降到13 000 mg/L左右。混凝预处理后的神经节苷脂生产废水经48 h厌氧和84 h好氧生物处理，COD值进一步下降到600 mg/L左右。然后向每升生化出水中加入2～3 mmol Fe³⁺,通过化学沉淀作用除去其中的磷酸盐，过量的Fe³⁺作为后续类Fenton氧化的催化剂。当H₂O₂(30％)用量为2～3 mL/L时，最终出水的COD值可以达到国家一级排放标准。     

Prospect of recovering phosphorus in magnesium slag-packed wetland filter

Phosphorus recovery from wastewater not only reduces the unbearable impacts of excessive nutrient discharge on environmental systems but also favor the reuse of phosphorus resource. Based on the mechanism as well as technical analysis for major phosphorus recovery techniques including struvite precipitation and wetland substrate adsorption, a novel magnesium slag-packed wetland filter and corresponding operational procedures are proposed, which aim to reduce the dependence of using magnesium-containing chemical reagent as magnesium sources for struvite precipitation, and improve the accumulation and recovery performance for struvite precipitation within porous wetland substrate. Results from preliminary experiments indicated that magnesium slag particles with approximately 2 mm in diameter can recover 43.20–72.39% phosphorus from 1–25 mol/L PO₄ ^3? solution, and the presence of 5–50 mol/L NH₄ ⁺ contributed to 11.71–29.11% enhancement of phosphorus recovery mainly due to struvite precipitation. The detected generation of struvite via XRD spectrum analysis partly demonstrated the potential of phosphorus recovery in magnesium slag-packed wetland filter. The proposed phosphorus recovery technology is free of secondary pollution and solid waste generation; phosphorus-saturated (mainly due to struvite precipitation and adsorption) magnesium slag particles can be potentially used as phosphorus fertilizer and thus partly solved the traditional shortages of disposing phosphorus-saturated substrate due to low phosphorus contents.     

高浓度钻井废水的混凝-催化氧化处理

以华北油田某深井的高浓度钻井废水(COD高达14 460.0 mg/L)为研究对象,提出了酸化-混凝-催化氧化-吸附的组合处理工艺。重点研制了钻井废水催化氧化处理催化剂(镍基催化剂),通过实验确定了最佳工艺参数条件。着重考察了催化氧化处理的工艺条件,在pH值为4,次氯酸钙投加量为4.4 g/L,催化剂投加量为1.6 g/L的条件下COD降至403.5 mg/L,进一步吸附处理后COD降至139.9 mg/L、色度为30倍、石油类含量为3.8 mg/L、pH为8.0和SS浓度为52mg/L,最终出水水质达到《污水综合排放标准》(GB 8978-1996)二级标准,处理成本为84.8元/m3。     

Nitrogen and phosphorus removal for swine wastewater by ammonium crystallization and intermittent aeration process

Abstract

A process on crystallized precipitation of ammonium by adding magnesium salt and phosphate was carried out to improve C/N ratio in swine wastewater. After completion of crystallized precipitation of ammonium, an intermittent aeration process with aeration and non‐aeration periods alternated at interval of 1:1 hr day^‐1 is used for the improved swine wastewater (T‐N/BOD=0.14: BOD=8200 mg/liter and T‐N=1166 mg/liter). The results obtained from the experiment show that the removal ratios of T‐N and NH₄‐N are 91% and 99%, respectively. T‐P is not removed, while the removal ratio of PO₄‐P is 60% as 3% of CaCl₂ liquid is added. The results also indicate that dilution with water is effective to improve the removal of phosphorus even if raw swine wastewater contains high concentrations of T‐N, T‐P, BOD, and TOC.     

Repeated use of MAP decomposition residues for the removal of high ammonium concentration from landfill leachate

The residues of magnesium ammonium phosphate (MAP) decomposed by heating under alkali conditions were repeatedly used as the sources of phosphate and magnesium for the removal of high ammonium concentration from landfill leachate. Up to 96% of ammonium in MAP powder could be released under the following conditions: NH4(+):OH- molar ratio, 1:1; temperature, 90 degrees C; heating time, 2 h. Fourier transform infrared spectra and X-ray diffraction analysis of MAP before and after heating demonstrated that MAP was mainly transformed to amorphous magnesium sodium phosphate (MgNaPO4), which makes it possible for the NH4(+) to replace Na+ in MgNaPO4 to form more stable struvite. Successful ammonium removal was achieved by using the MAP decomposition residues as the sole phosphate and magnesium sources. The ammonium removal decreased gradually following the increase of MAP reuse cycles, and in the 6th cycle, ammonium removals of 84% and 62% were achieved for synthetic wastewater and landfill leachate, respectively. Analysis of the surfaces of MAP powders acquired at different reuse cycles using scanning electron microscopy with energy dispersive X-ray suggested that the existence of calcium, kalium and aluminum ions in landfill leachate might have inhibited the formation of MAP through competition with ammonium ions for phosphate ions. It is estimated that reuse of MAP for 3 cycles could save about 44% chemical costs.     

掺Al-TiO2改性膨润土去除微污染水中COD和NH4-N

采用掺Al-TiO2作为改性剂制备改性膨润土,考察了微波辐射功率、辐射时间、TiO2改性剂用量、铝盐掺杂量、pH值对微污染水中COD和NH4-N去除效果的影响。实验表明,微波辐射功率为460 W,辐射时间为8 min,TiO2改性剂用量为1.3 mmol/g,铝盐掺杂量为0.2 mmol/g为最佳制备条件。pH值为6.0,改性膨润土投加量为40 mg/L,沉淀时间为30min时,对微污染水中初始浓度15 mg/L的COD和5 mg/L的NH4-N去除率分别达到92%和59%以上。     

UV/Fenton技术处理某工厂高浓度乳化油废水

研究了UV/Fenton技术对高浓度金属清洗乳化油废水的处理效果,考察了亚铁与双氧水浓度、pH、反应时间和搅拌对COD去除效果的影响。实验结果表明,UV/Fenton技术对高浓度乳化油废水(COD平均浓度为35 000 mg/L)具有较高的去除效果,最佳工艺条件为:亚铁与双氧水浓度分别为2 400 mg/L和6 000 mg/L,pH为3,经过2 h反应,COD可降低至1 050 mg/L,去除率为97%。搅拌会降低COD的去除率。研究表明,UV/Fenton技术对高浓度乳化油废水具有很好的降解效果,且药品消耗较低,为目前此类高浓度有机废水的处理提供了技术参考。     

Fenton氧化-序批式膜生物反应器耦合处理干法腈纶废水

采用Fenton氧化-序批式膜生物反应器(SBMBR)组合工艺处理干法腈纶废水。结果表明,在废水初始pH值为3.0,H2O2投加量为90.0 mmol/L,Fe2+投加量为20.0 mmol/L,反应时间为2.0 h的条件下,Fenton氧化预处理对腈纶生产废水的COD去除率达到47.0%以上,COD由1 091 mg/L降至560 mg/L,废水的BOD5/COD由0.32升至0.69,废水的可生化性得到显著提高。Fenton处理出水与丙烯腈废水等比例混合后,采用SBMBR进行生化处理,在水力停留时间为24 h,90 min缺氧/150 min好氧交替运行的条件下,COD、NH4+-N和TN的平均去除率分别为71.7%、97.2%和47.4%,碳源不足是限制TN去除效果的主要影响因素。在无外加碳源的条件下,组合工艺处理后出水COD和NH4+-N浓度分别为117 mg/L和1.7 mg/L,出水水质可以稳定达到国家一级排放标准(GB8978-1996)。     

酸性条件下剩余污泥中Ca2＋和Mg2＋溶出对磷回收的影响

为了在酸性条件下实现剩余污泥中磷的高效回收，对pH=3时剩余污泥水解酸化过程中氨氮、正磷酸盐和钙镁离子的溶出现象以及磷回收进行了研究分析。结果表明：当pH=3时，所溶出的氨氮、镁离子和钙离子与磷酸盐的摩尔比均大于1，能满足采用鸟粪石沉淀法或者羟磷灰石沉淀法回收磷的要求；但所溶出的钙镁离子的摩尔比大于1，会对鸟粪石沉淀法回收磷的顺利进行有较大影响；有无外加镁剂对磷回收率影响不大。采用改型后的镁型强酸性阳离子交换树脂进行离子交换可以得到较高纯度的鸟粪石沉淀产品，通过XRD检测其纯度为95％以上。     

碳酸根对磷酸钙沉淀反应回收磷的影响

以模拟的厌氧消化液为处理对象，通过小试实验，考察不同初始磷浓度Cp、Ca／P物质的量比、pH和温度下，碳酸根（CO3 2-）对磷酸钙沉淀反应回收磷的影响；利用扫描电镜（SEM）、x射线衍射仪（XRD）和傅里叶变换红外光谱（FT．IR）对沉淀产物进行表征。结果表明，高浓度的CO3 2-对以磷酸钙沉淀反应去除和回收磷的效率影响较大；Cp相同时，CO3 2-浓度（CCO3^2-）越大，P的去除率越低，低C，（20mg／L）时尤为显著；当CCO3^2-相同时，随着Cp的增大，反应速率加快，P的去除率逐渐升高，但升高幅度越来越小；增大Ca／P比和pH能提高P的去除率，降低CO3 2-对磷酸钙沉淀反应的抑制作用，综合考虑实际效果，应选择Ca／P比为3．33，pH为9．0作为适宜的反应条件；升高温度对降低CO3 2-对磷酸钙沉淀反应的抑制作用贡献不大。在Cp为60ITIg／L，Ca／P比为1．67，pH为9．0，温度为20℃的条件下，当CCO3^2-为0时，得到的沉淀产物主要为羟基磷灰石HAP；当CCO3^2-为30mmol／L时，得到的沉淀产物为磷酸钙和碳酸合磷灰石的混合物。     

MAP法沉淀回收装置的运行条件优化研究

采用一种简易的MAP回收装置,研究了间歇运行条件下反应时间和曝气量对MAP法除磷效果的影响,确定出最佳反应时间为90 min,最佳曝气量为1.2 L/min,相应的除磷率可达98.26%,沉淀回收率为74.54%。当增加一个漏斗形隔板分离反应区和沉淀区并连续运行时,除磷率和沉淀回收率分别为92.11%和63.66%。当不投加镁盐和铵盐而仅调控实际污泥脱水滤液的pH值为9.8时,其连续运行的平均除磷率和MAP回收率分别可达95.16%和70%,运行性能比较稳定。     

絮凝-Fenton试剂氧化处理印染废水

采用Fenton试剂对某染袜厂2种印染废水(印染红和印染蓝)进行处理。考察了硫酸亚铁投加量、双氧水投加量、反应时间及pH值对印染废水的色度及COD去除率的影响,通过正交实验确定了Fenton试剂处理该废水的最佳操作条件为:反应时间30 min、双氧水(30%)投加量4 mL/L、硫酸亚铁投加量300 mg/L、pH值为4左右。在最佳条件下,印染蓝废水经氧化处理后COD去除率大于80%,色度去除率95%以上;印染红废水需经絮凝预处理后再用Fenton试剂氧化处理,其脱色率达到了99.6%,COD去除率为91.2%,出水COD浓度为96 mg/L,可达标排放。     

曝气生物滤池中碳和氮代谢特性

用充填陶瓷滤料的曝气生物滤池研究碳和氮代谢特性.曝气生物滤池进水氨氮为52 mg/L左右、COD为100 mg/L左右和回流比为200%时,经过20多d的运行,出水氨氮小于0.05 mg/L、COD小于25 mg/L、亚硝态氮为4.7 mg/L和硝态氮为7.1 mg/L,COD去除率达75%,氨氮去除率达99.9%,总氮去除率达78%;过大和过小的回流比对曝气生物滤池的运行性能都是不利的.研究成果可以应用于一般城市污水以及含低COD、高氨氮工业废水的处理.