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 x 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。     

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.     

Simultaneous removal of phosphorus and potassium from synthetic urine through the precipitation of magnesium potassium phosphate hexahydrate

This study investigated the simultaneous removal of P and K from synthetic urine through the precipitation of magnesium potassium phosphate hexahydrate (MPP, MgKPO₄·6H₂O) in bench-scale experiments. Results show that the removal efficiencies of P and K are mainly determined by the solution pH and the molar ratio of Mg:K:P. Co-precipitation of struvite-type compounds, i.e., magnesium ammonium phosphate hexahydrate (MAP, MgNH₄PO₄·6H₂O), magnesium sodium phosphate heptahydrate (MSP, MgNaPO₄·7H₂O), and MPP, was confirmed by analysis of the solid precipitates using a Scanning Electron Microscope/Energy Dispersive X-ray Apparatus and an X-ray Diffractometer. The co-precipitation significantly influenced the removal of K. As much ammonium as possible should be removed prior to MPP precipitation because MAP had higher tendency to form than MPP. The inevitable co-precipitation of MPP and MSP resulted in the addition of more MgCl₂·6H₂O and Na₂HPO₄·12H₂O to obtain the high removal of K. In total, the removal efficiencies of P and K were 77% and 98%, respectively, in the absence of ammonium when pH was 10 and the molar ratio of Mg:K:P was 2:1:2. The results indicate that the MPP precipitation is an efficient method for the simultaneous removal of P and K to yield multi-nutrient products.     

Modeling the crystallization of magnesium ammonium phosphate for phosphorus recovery

The crystallization of magnesium ammonium phosphate (MAP) is one of the main processes for recovering P and N from wastewater. Chemically defined solution systems were designed; the saturation indices (SIs) of the solution systems with respect to MAP were derived by using a geochemical aqueous model Program, PHREEQC 2.11; the effects of the solution conditions were evaluated using thermodynamic theories. The concentrations of P and Mg in the tested solutions were 10-600 mg l(-1) and 24-720 mg l(-1), respectively, the molar ratios of N/P and pH values of the solutions varied in the ranges of 1-40 and 6.0-12.0, respectively. The temperature of all the tests was set at 25 degrees C. The test results show that the SI value of MAP is the logarithmic functions of the concentrations of P, ammonium-N and Mg, and increases with the increase of the concentration of each element. The SI value of MAP is a polynomial function of pH value of the solution, and the optimum pH value for the crystallization of MAP is 9.0 but increases slightly with the increase of the N/P. Moreover, the SI value of MAP is a power law function of the ionic strength of solutions but decreases with its increase. The adjustment of the Mg concentration and the control of solution pH are two effective methods for the control of the crystallization of MAP. The results obtained from the research can be used to guide the design and control of MAP crystallization process for the removal and recovery of P.     

磷酸铵镁沉淀法预处理垃圾渗滤液

探讨了用磷酸铵镁沉淀法预处理垃圾渗滤液时,沉淀剂种类、pH值、物质摩尔配比和反应时间等因素对氨氮去除效果的影响。得出了处理氨氮浓度为2 677.34 mg/L的垃圾渗滤液时,在兼顾所用镁盐量尽量低和处理出水氨氮或磷酸盐的残留量都比较低的较佳实验条件为:沉淀剂种类为:MgSO4.7H2O和Na2HPO4.12H2O,反应时间为20 min,pH=9.5,n(Mg)∶n(P)∶n(N)=1.3∶1.15∶1.0。在较佳实验条件下,垃圾渗滤液的NH3-N去除率为97.05%,处理出水PO34--P含量为8.35 mg/L,NH3-N含量为75.86 mg/L。对所得沉淀物进行了成分分析和X-衍射光谱、扫描电镜表征,表明大部分沉淀物为磷酸铵镁物质。     

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。     

共存杂质对磷酸铵镁结晶法回收磷的影响研究

研究用磷酸铵镁（MAP）结晶法去除、回收废水中的磷,分析含磷废水中各类共存杂质对MAP法去除、回收磷的影响。结果表明,废水中无机钙离子的存在可提高磷的去除率,而大分子有机物杂质的存在会使磷的去除率显著降低,小分子有机物对磷的去除基本无影响。在反应体系中引入外来晶种烟煤、石英砂和铁屑可显著提高低浓度含磷废水磷的去除效率,其中娴煤作为晶种的效果最明显。     

不同Ca/P比下碳酸根对磷酸钙沉淀反应回收磷的影响

以模拟污水处理厂污泥厌氧消化液为处理对象,进行磷酸钙沉淀除磷小试实验,考察了不同Ca/P物质的量比下碳酸根(CO2-3)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(FTIR)对沉淀产物进行表征。结果表明,磷酸钙沉淀反应是一个快速过程,CO2-3的存在并未改变这一显著特征。磷酸钙沉淀反应过程中,CO2-3的存在降低了磷的去除率,改变了沉淀物形貌、结构和组分;实验设定范围内,磷酸钙的过饱和度越高,越难形成晶体态羟基磷灰石((Ca5(PO4)3OH,HAP);当pH值为9.0,Ca/P比为1.67时,CO2-3取代HAP晶格中的PO3-4,形成碳磷灰石(CHAP);当pH值为9.0,Ca/P比为3.33和5.01时,CO2-3和PO3-4之间竞争,形成碳酸钙(CaCO3);增大Ca/P能有效提高磷的去除率,降低CO2-3对磷酸钙沉淀反应的抑制作用,但综合考虑实际效果,选择Ca/P比为3.33作为适宜的反应条件。     

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.     

鸟粪石结晶法去除垃圾渗滤液中NH_4~+-N的效果研究

研究了鸟粪石结晶法对经混凝预处理后的垃圾渗滤液中NH4+-N的去除效果,考察了不同影响因素对NH4+-N去除效果的影响,并进行了磷酸铵镁(MgNH4PO4·6H2O,简称MAP)沉淀的表征及成分分析,并提出了反应后溶液中Mg2+、PO43-及MAP的回收利用办法。结果表明,反应的最佳条件为:pH8.5～9.5,Mg2+∶NH4+∶PO34-(摩尔比)=1.1∶1.0∶1.3,反应温度30℃,反应时间为25 min时,此时NH4+-N的去除率达94.70%;最佳沉淀剂投加组合为MgCl2.6 H2O与Na2HPO4·12H2O;pH为9.0时生成的沉淀符合典型MAP沉淀的晶体结构,生成的沉淀大部分为MAP,且没有氰化物、酚等有害物质的检出,而pH为10.5时生成的沉淀由许多疏松的微小沉淀颗粒组成,排列较杂乱,影响了沉淀的纯度。利用鸟粪石结晶法去除混凝预处理后的垃圾渗滤液中NH4+-N技术可行,经济效益合理,具有广阔的应用前景。     

Phosphorus recovery from fosfomycin pharmaceutical wastewater by wet air oxidation and phosphate crystallization

Fosfomycin pharmaceutical wastewater contains highly concentrated and refractory antibiotic organic phosphorus (OP) compounds. Wet air oxidation (WAO)-phosphate crystallization process was developed and applied to fosfomycin pharmaceutical wastewater pretreatment and phosphorus recovery. Firstly, WAO was used to transform concentrated and refractory OP substances into inorganic phosphate (IP). At 200 °C, 1.0 MPa and pH 11.2, 99% total OP (TOP) was transformed into IP and 58% COD was reduced. Subsequently, the WAO effluent was subjected to phosphate crystallization process for phosphorus recovery. At Ca/P molar ratio 2.0:1.0 or Mg/N/P molar ratio 1.1:1.0:1.0, 99.9% phosphate removal and recovery were obtained and the recovered products were proven to be hydroxyapatite and struvite, respectively. After WAO-phosphate crystallization, the BOD/COD ratio of the wastewater increased from 0 to more than 0.5, which was suitable for biological treatment. The WAO-phosphate crystallization process was proven to be an effective method for phosphorus recovery and for fosfomycin pharmaceutical wastewater pretreatment.     

磷酸钙盐结晶除磷工艺性能研究

研究了主要工艺条件pH和Ca/P对磷酸钙盐结晶除磷工艺性能的影响。通过分批实验,建立了磷去除率与pH之间的指数函数关系以及磷去除率与Ca/P之间的对数函数关系。连续运试表明,在pH=9.0、Ca/P=2的条件下,磷酸钙盐结晶除磷反应器的容积负荷为1.10 kg P/(m3.d),磷去除率为51%。灵敏度分析表明,pH对磷去除率的影响大于Ca/P,将Ca/P提高至6,容积负荷提高至1.60 kg P/(m3.d),磷去除率提高至74.3%;将pH提高至10.0,容积负荷提高至1.80 kg P/(m3.d),磷去除率提高至83.5%。工艺操作上可选pH作为优先控制对象。     

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。     

复合型聚合硅酸絮凝剂的制备及其除浊除磷性能研究

在聚合硅酸中同时引入铁、镁或铁、钙2种金属离子,制成复合型聚合硅酸絮凝剂;研究了其除浊、除磷的最佳絮凝条件,包括絮凝剂投加量、水样pH值对浊度和磷去除率的影响;采用喹啉重量法测定了各种絮凝剂形成的絮体中磷的含量.结果表明,当铁磷摩尔比为2.5～3.0,pH值为7.0～8.5时,对浊度和磷的去除率最高,均达99.0%以上,聚合硅酸镁铁(PSAMF)絮凝剂适合用于磷回收.     

Phosphate removal from digested sludge supernatant using modified fly ash

The removal of phosphate in digested sludge supernatant by modified coal fly ash was investigated in this study. Modification of the fly ash by the addition of sulfuric acid could significantly enhance its immobilization ability. The experimental results also showed that adsorption of phosphate by the modified fly ash was rapid with the removal percentage of phosphate reaching an equilibrium of 98.62% in less than 5 minutes. The optimum pH for phosphate removal was 9 and the removal percentage increased with increasing adsorbent dosage. The effect of temperature on phosphate removal efficiency was not significant from 20 to 40 degrees C. X-ray diffraction and scanning electron microscope analyses showed that phosphate formed an amorphous precipitate with water-soluble calcium, aluminum, and iron ions in the modified fly ash.     

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.     

利用白云石回收污泥厌氧消化液中的磷

为经济有效地从污泥厌氧消化液中回收磷,构建了以白云石提供钙镁源的磷回收方法,探讨了磷回收的工艺条件与效果。通过盐酸酸化厌氧消化液以降低其碳酸盐含量,同时利用白云石溶于冷稀盐酸的特性使其钙镁缓慢释放到酸化的厌氧消化液中形成第一步磷回收体系,考察体系酸化pH、白云石与厌氧消化液的固液比以及反应pH对白云石的钙镁释放和磷回收效果的影响;第一步磷回收后的上清液为第二步厌氧消化液磷回收提供钙镁源,研究投加钙磷摩尔比对磷回收效果的影响。实验结果表明,当固液比为5.0时,在酸化pH为4.0～4.5且酸化溶出时间为10 h以及反应pH为9.0的条件下,第一步磷回收产物以磷酸钙盐沉淀为主,厌氧消化液磷回收率及回收产物含磷率（以P2O5计）分别达到99.43%和38.49%;第一步磷回收后的上清液按一定的钙磷摩尔比投加到酸化后的厌氧消化液中进行第二步磷回收,当投加钙磷摩尔比为0.20时,在反应pH为9.0的条件下,回收产物同时含有磷酸钙盐和磷酸铵镁,厌氧消化液中氮、磷回收率分别达到13.19%和90.90%,回收产物氮、磷含量（以P2O5计）分别为0.26%和39.58%;经XRD、XRF、ICP及SEM等分析表征,2步磷回收的产物以磷酸钙盐和磷酸铵镁为主要成分,杂质少。研究表明,利用白云石为钙镁源,通过分别构建不同的磷回收体系可以分步从污泥厌氧消化液中经济有效地回收磷,且磷回收率和回收产物含磷率高。     

改性粉煤灰处理低浓度含磷废水的研究

以酸改性粉煤灰为吸附剂,处理低质量浓度(1 mg/L左右)磷酸盐溶液,探讨了改性剂的种类、改性剂用量、吸附剂用量、反应时间、pH以及温度对除磷效果的影响.结果表明:(1)经过酸改性后粉煤灰的磷去除率显著提高,而且硫酸改性粉煤灰的除磷效果更好,磷去除率最高可达97.68％.(2)最佳条件:选择硫酸用量为5 mL/g进行改性,硫酸改性粉煤灰投加量为2.0g,反应时间为60 min,pH为7.2～10.8,温度为25℃(即室温).(3)改性粉煤灰对磷的吸附更符合Freundlich吸附等温模型,既有物理吸附,也有化学吸附,并以Ca、Mg氧化物与磷形成磷的沉淀物为主.     

Effects of solution conditions on the precipitation of phosphate for recovery. A thermodynamic evaluation

To understand the effects of solution conditions on the precipitation of calcium phosphates from wastewater for recovery, a computer programme PHREEQC was employed to calculate the speciation and saturation-index (SI) with respect to hydroxyapatite of a chemically defined precipitation system, which contains phosphate of 1–200 mg P/l, with Ca/P molar ratios of one to 10 times of the stoichiometric calcium to phosphorus molar ratio of hydroxyapatite, at a pH range of 7.0–11.0. The results show that the SI is respectively the logarithmic function of the phosphate concentration and the calcium concentration, increasing with the increase of either of them; the SI is a polynomial function of the solution pH value and increases with its increase, and the effect of solution pH value is due to its influence on base uptake of the precipitation reaction and the speciation of phosphate and calcium ions; the SI is also a logarithmic function of the solution ionic strength but decreases with its increase; at the temperature range of 5–30 °C the SI increases linearly with solution temperature and the effect of temperature is also due to its influence on the speciation of phosphate and calcium ions.