工艺条件对磷回收过程中鸟粪石沉淀颗粒粒径的影响

在鸟粪石沉淀法回收废水中磷的过程中,鸟粪石颗粒的大小将直接影响其沉淀的速率,进而影响鸟粪石的沉淀效果和磷的回收率。本文采用激光粒度分析仪测定鸟粪石的平均粒径,详细考察在小型连续搅拌反应-沉淀磷回收装置中不同的工艺条件下鸟粪石颗粒粒径的变化规律,并结合Stokes公式计算鸟粪石颗粒在废水出口处的沉降速率,为沉淀池的设计提供参考依据。结果表明:鸟粪石的平均粒径在12～25μm之间,沉降速率在5.46×10-5～2.37×10-4m/s之间。随着反应室水力停留时间的延长,鸟粪石颗粒的粒径逐渐增大,当停留时间超过18 min时,颗粒的粒径基本不变;随着沉淀室水力停留时间的延长,鸟粪石颗粒的平均粒径缓慢增大,当停留时间超过70 min后颗粒粒径的变化不大;鸟粪石颗粒的平均粒径在一定程度上受废水中磷初始浓度变化的影响,在磷初始浓度为62～128 mg/L时颗粒的粒径变化不大,当磷浓度为496 mg/L时粒径有较大增加,此时鸟粪石颗粒的沉降速率也大幅度增加;鸟粪石颗粒的平均粒径受pH值的影响不大;随氮磷摩尔比的增大,鸟粪石颗粒的平均粒径略有增加;随镁磷摩尔比的增大,鸟粪石颗粒的平均粒径逐渐减小,沉降速率则有明显的下降。     

Phosphorus leaching in soils amended with piggery effluent or lime residues from effluent treatment

Phosphorus (P) in wastes from piggeries may contribute to the eutrophication of waterways if not disposed of appropriately. Phosphorus leaching, from three soils with different P sorption characteristics (two with low P retention and one with moderate P retention) when treated with piggery effluent (with or without struvite), was investigated using batch and leaching experiments. The leaching of P retained in soil from the application of struvite effluent was determined. In addition, P leaching from lime residues (resulting from the treatment of piggery effluent with lime to remove P) was determined in comparison to superphosphate when applied to the same three soils. Most P was leached from sandy soils with low P retention when effluent with or without struvite was applied. More than 100% of the filterable P applied in struvite effluent was leached in sandy soils with low P retention. Solid, inorganic forms of P (struvite) became soluble and potentially leachable at pH<7 or were sorbed after dissolution if there were sufficient sorption sites. In sandy soils with low P retention, more than 39% of the total filterable P applied in recycled effluent (without struvite) was leached. Soil P increased mainly in surface layers after treatment with effluent. Sandy soils pre-treated with struvite effluent leached 40% of the P retained in the previous application. Phosphorus decreased in surface layers and increased at depth in the soil with moderate P retention after leaching the struvite effluent pre-treated soil with water. The soils capacity to adsorb P and the soil pH were the major soil properties that affected the rate and amount of P leaching, whereas the important characteristics of the effluent were pH, P concentration and the forms of P in the effluent. Phosphorus losses from soils amended with hydrated lime and lime kiln dust residues were much lower than losses from soils amended with superphosphate. Up to 92% of the P applied as superphosphate was leached from sandy soils with low P retention, whereas only up to 60% of the P applied in lime residues was leached. The P source contributing least to P leaching was the lime kiln dust residue. The amount of P leached depended on the water-soluble P content, neutralising value and application rate of the P source, and the pH and P sorption capacity of the soil.     

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。     

Adsorption and precipitation of tetracycline with struvite.

The interaction of tetracycline with struvite during adsorption and precipitation processes was investigated. Tetracycline removal by adsorption was affected by solution pH, contact time, and struvite concentration. The lowest tetracycline removal (8.4%) was observed at pH 7.7, the dissociation constant (pKa2) of tetracycline. Because of the electrostatic repulsion, the amount of tetracycline adsorbed on the surface was low. The small amount of adsorption was the result of surface complexation between tetracycline ions and metal ions. Calcium (Ca2+) ions in the adsorbent enhanced the binding of tetracycline. Freundlich (KF: 0.04, n: 1.49) and Redlich-Peterson (KR: 0.08, alphaR: 0.98, betaR: 0.49) models best defined the equilibrium data. In the case of struvite precipitation, approximately 22% of tetracycline was removed as a result of binding to struvite alongside struvite formation.     

工艺条件对鸟粪石晶体的粒径和沉降速度的影响

采用激光粒度仪实验测定了小型套管式空气曝气填料层磷回收装置中不同条件下生成的鸟粪石晶体的体积平均粒径,考察了其变化规律,并结合Stokes公式计算了晶体的沉降速率,同时考虑鸟粪石晶体形状的影响,进行了相应的修正。实验结果表明,鸟粪石的粒径在10—200μm之间,主要集中于20～100μm;在磷回收装置中添加填料并通人空气有利于增大鸟粪石晶体的粒径和沉降速度,无填料无空气时和有填料有空气时的平均粒径分别在30～55μm和40～65μm之间。随着pH值的增大,鸟粪石晶体的粒径和沉降速度逐渐增大,但当pH大于9．0后,鸟粪石晶体的粒径和沉降速度又逐渐减小;氮磷比值从1：1增大到2：1,鸟粪石晶体的粒径和沉降速度小幅度增加,氮磷比进一步增大,鸟粪石晶体的粒径和沉降速度基本不变;镁磷摩尔比在1：1—1．2：1的范围内时,鸟粪石晶体的平均粒径和沉降速度随镁磷比的增大而增大;镁磷摩尔比大于1．2：1后,鸟粪石晶体的平均粒径和沉降速度随镁磷比的增大逐渐减小;初始磷浓度越高,鸟粪石晶体的平均粒径和沉降速度越大。     

Effect of seeding materials and mixing strength on struvite precipitation.

Struvite precipitation has increasing interest as a technology for removing and recovering phosphorus from wastewater streams. Many chemical factors have been studied, such as optimum pH values and component-ion molar ratios, yet, understanding of physical aspects is lacking. Two physical parameters were tested: (1) seeding material addition and (2) mixing. Objectives were to evaluate three seeding materials and to optimize mixing conditions for struvite-crystal precipitation, growth, and subsequent sedimentation. Results confirm that mixing strength and proper seeding materials increase crystal size and improve settleability. For unseeded solutions, optimum phosphorus removal was achieved at a mixing strength of G = 76 s(-1). Struvite crystals that were added as the seeding material provided the best performance with respect to phosphorus removal and crystal-size distribution. Overall, this study provided information to improve the practical application of struvite precipitation as a phosphorous-treatment technology for wastewaters, while generating a marketable slow-release fertilizer as a product.     

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.     

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.     

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.     

Significance of design and operational variables in chemical phosphorus removal

Batch and continuous experiments using model and real wastewaters were conducted to investigate the effect of metal salt (ferric and alum) addition in wastewater treatment and the corresponding phosphate removal from a design and operational perspective. Key factors expected to influence the phosphorus removal efficiency, such as pH, alkalinity, metal dose, metal type, initial and residual phosphate concentration, mixing, reaction time, age of flocs, and organic content of wastewater, were investigated. The lowest achievable concentration of orthophosphate under optimal conditions (0.01 to 0.05 mg/L) was similar for both aluminum and iron salts, with a broad optimum pH range of 5.0 to 7.0. Thus, in the typical operating range of wastewater treatment plants, pH is not a sensitive indicator of phosphorus removal efficiency. The most significant effect for engineering practice, apart from the metal dose, is that of mixing intensity and slow kinetic removal of phosphorus in contact with the chemical sludge formed. Experiments show that significant savings in chemical cost could be achieved by vigorously mixing the added chemical at the point of dosage and, if conditions allow, providing a longer contact time between the metal hydroxide flocs and the phosphate content of the wastewater. These conditions promoted the achievement of less than 0.1 mg/L residual orthophosphate content, even at lower metal-to-phosphorus molar ratios. These observations are consistent with the surface complexation model presented in a companion paper (Smith et al., 2008).     

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。     

Performance of a submerged membrane bioreactor system for biological nutrient removal.

A pilot submerged membrane bioreactor coupled with biological nutrient removal was used to treat the primary effluent at a municipal wastewater treatment plant. Long-term experiments were conducted by varying hydraulic retention time from 6 to 8 hours and solids retention time from 20 to 50 days, respectively. The performance was assessed by monitoring key wastewater parameters, including chemical oxygen demand (COD), nitrogen, and phosphorus concentration in individual anoxic, anaerobic, aerobic, and membrane separation zones. Results showed that the tested system can consistently achieve COD, nitrogen, and phosphorus removal efficiencies at 80 to 98%, 70 to 93%, and 89 to 98%, respectively. Effluent COD remained low as a result of efficient solid retention, even though there was great variation in influent quality. However, total nitrogen increased proportionally with influent concentration. At a 50-day solids retention time, higher COD and nitrogen oxides specific utilization rates in the anoxic zone resulted in a high production of nitrogen oxides in the subsequent aerobic zone.     

Struvite precipitation by the dissolved CO2 degasification technique: impact of the airflow rate and pH

In the present work, struvite precipitation was provoked by the dissolved CO(2) degasification technique where precipitation occurred following the degassing of the CO(2) by atmospheric air. The impact of the airflow rate and initial solution pH on struvite precipitation were assessed. For initial solution pH<6.5, no precipitation was observed. For initial solution pH>6.5, the phosphorus removal through struvite precipitation could be improved by increasing the airflow rate up to 25 L min(-1), or by increasing the initial pH for higher airflow rates. Compared to traditional techniques of struvite precipitation such as stirring and aeration, the dissolved CO(2) degasification technique is promising since a high amount of phosphorus (approximately 78%) could be removed at relatively short experiment time.     

Study on particulates and volatile organic compounds removal with TiO2 nonwoven filter prepared by electrospinning

In this study, polyvinyl alcohol (PVA) and titania (TiO₂) Degussa P-25 were mixed to generate TiO₂ nonwoven filters using electrospinning. The wires of titanium dioxide and the nonwoven binding titania nanofibers were formed using 14 kV voltage and a distance of 15 cm. A single-factor experimental method was used to investigate the effects of parameters such as initial concentration, retention time, and light source on acetone removal by nonwoven binding titania nanofibers. Furthermore, the effects of parameters such as gas pressure, particle size, initial concentration, and retention time on the removal of particulates were also assessed. The results showed that the degradation efficiency increased with decreasing initial concentrations and increasing retention time. The best operational conditions during this study for the removal of acetone using the TiO₂ nonwoven filters were a retention time of 100 sec, initial acetone concentration of 250 ppm, and ultraviolet (UV) light source of 254 nm. Under those conditions, 99% acetone removal efficiency was obtained. In addition, 90% particulate matter removal efficiency was reached when the particulate size was greater than 200 nm and the reaction time was longer than 5 minutes. The prepared TiO₂/nanofiber has good performance for volatile organic compounds (VOCs) and particulate removal at the same time.

Implications: In this study, polyvinyl alcohol (PVA) and titania (TiO₂) Degussa P-25 were mixed to generate TiO₂ nonwoven filters using electrospinning. The results showed that the optimum operating conditions for the removal of acetone using the TiO₂ nonwoven filters were a retention time of 100 sec, initial acetone concentration of 250 ppm, and UV light source of 254 nm. Under those conditions, 99% acetone removal efficiency was obtained.     

预涂动态膜强化渗透与截留性能研究

以二氧化钛粉体材料为涂膜剂,陶瓷管为基膜制备预涂动态膜,引入通量增强系数Zi和截留增强系数Fi研究了预涂动态膜制备条件对其强化渗透与截留性能的影响,并用SEM电镜对预涂动态膜和基膜表面形貌进行表征。结果表明:制备的预涂动态膜表面均匀密实,其孔径低于基膜平均孔径。预涂动态膜的渗透与截留性能随涂膜液pH值的增加而增加,在跨膜压差低于0.2 MPa、错流速度低于1.5 m/s,涂膜时间少于30 m in和涂膜液浓度低于0.4 g/L范围内,提高这些参数值有利于提高预涂动态膜的渗透与截留性能,超出此范围时,提高这些参数值对增强其渗透与截留性能的效果已不明显,其中错流速度的影响相对小些。跨膜压差为0.2 MPa,错流速度为1.5 m/s,涂膜时间30 m in,涂膜液浓度和pH值分别为0.4 g/L和10.2时为最佳制备条件。     

Prevention of struvite scaling in digesters combined with phosphorus removal and recovery--the FIX-Phos process

The fixation of phosphorus (FIX-Phos) combines struvite prevention and phosphorus recovery by the addition of calciumsilicatehydrate (CSH) particles into the anaerobic digester. The CSH fixates phosphorus as calcium phosphate and reduces the phosphorus concentration in the sludge water that allows for control of struvite formation. The phosphorus-containing recovery product can be separated and recovered from the digested sludge. In pilot plant experiments, 21% to 31% of phosphorus contained in digested sludge could be recovered when CSH was added at concentrations of 2 g/L to 3.5 g/L to a mixture of primary sludge and waste activated sludge (WAS) from enhanced biological phosphorus removal. The recovery product contained few heavy metals and a phosphorus content of 18 wt % P2O5, which allows for recycling as fertilizer. The fixation of phosphorus within the digester may increase wastewater sludge dewaterability. The phosphorus recycle stream to the headworks of the wastewater treatment plant is reduced.     

Fate of methidathion residues in biological waste during anaerobic digestion

The aim of this study was to examine the fate of the organothiophosphorus pesticide methidathion during anaerobic digestion of biological waste. Three reactor experiments were conducted under various conditions of temperature, pH and retention time. The influence of pH and temperature as well as the partitioning between solid and aqueous phase were studied in batch experiments. The mesophilic (25, 35 degrees C) reactor experiments showed a decline to about 10% of the maximum methidathion concentration within 30-80 d. In the thermophilic (55 degrees C) reactor experiment, methidathion disappeared within 20 d. The batch experiments showed an abiotic hydrolysis of methidathion over the experiment period of 4 d, accelerated by alkaline conditions (pH 10.5 and 12.8) and high temperatures (55 degrees C). The hydrolysis was also noticeable at a neutral pH, while methidathion was most stable at weakly acid pH values. Methidathion bonded strongly to the biological waste, and the amount released into the water phase was below the maximum aqueous solubility. About 10% of methidathion remained non-extractable. High concentrations of dissolved organic carbon and yeast extract as a model substance for disintegrated cells further reduced the content of methidathion in the water phase, possibly caused by co-sorption to the solid organic matter.     

Indoor pollutant mixing time in an isothermal closed room: an investigation using CFD

We report on computational fluid dynamics (CFD) predictions of mixing time of a pollutant in an unventilated, mechanically mixed, isothermal room. The study aims to determine: (1) the adequacy of the standard Reynolds Averaged Navier Stokes two-equation (k−) turbulence model for predicting the mixing time under these conditions and (2) the extent to which the mixing time depends on the room airflow, rather than the source location within the room. The CFD simulations modeled the 12 mixing time experiments performed by Drescher et al. (Indoor Air 5 (1995) 204) using a point pulse release in an isothermal, sealed room mechanically mixed with variable power blowers. Predictions of mixing time were found in good agreement with experimental measurements, over an order of magnitude variation in blower power. Additional CFD simulations were performed to investigate the relation between pollutant mixing time and source location. Seventeen source locations and five blower configurations were investigated. Results clearly show large dependence of the mixing time on the room airflow, with some dependence on source location. We further explore dependence of mixing time on the velocity and turbulence intensity at the source location. Implications for positioning air-toxic sensors in rooms are briefly discussed.     

Effect of culture conditions on the formation of struvite by Myxococcus xanthus

The amount of struvite (MgNH₄PO₄·6H₂O) produced by Myxococcus xanthus as well as the culture parameter values (pH, total phosphorus, total Kjeldahl nitrogen) were dependent on the culture medium used. Struvite formation started during the exponential phase and the maximum concentration was observed at the beginning of stationary growth phase. The addition of each medium component to the liquid culture influenced the amount of crystal produced. This amount did not depend on the pH increase during the culture period. The moment of the bacterial growth phase, at which each medium component was added, influenced the struvite formation.