Microwave treatment and struvite recovery potential of dairy manure

Microwave digestion of liquid dairy manure was tested for the release of nutrients, such as orthophosphates, ammonia-nitrogen, magnesium, calcium and potassium, both with and without the aid of an oxidizing agent (hydrogen peroxide). The orthophosphate to total phosphorus ratio of the manure increased from 21% to greater than 80% with 5 minutes of microwave treatment. More than 36% of total chemical oxygen demand (t-COD) of the manure was reduced when microwave digestion was assisted with peroxide addition. In addition, the volatile fatty acids (VFAs) distribution shifted to simpler chain acids (acetic acid in particular) with an increase in operating temperature. In the second part of the study, digested manure with increased soluble phosphate was tested for the recovery of struvite (magnesium ammonium phosphate) at different pH. It was found that up to 90% of orthophosphate can be removed from the solution. Overall, it was concluded that the oxidizing agent-assisted microwave digestion process can be used upstream of anaerobic digestion, following which the anaerobically digested manure can be used for struvite recovery. Thus, this microwave digestion process presents the potential for enhanced efficiencies in both manure digestion and struvite recovery.     

Microwave treatment and struvite recovery potential of dairy manure

Microwave digestion of liquid dairy manure was tested for the release of nutrients, such as orthophosphates, ammonia-nitrogen, magnesium, calcium and potassium, both with and without the aid of an oxidizing agent (hydrogen peroxide). The orthophosphate to total phosphorus ratio of the manure increased from 21% to greater than 80% with 5 minutes of microwave treatment. More than 36% of total chemical oxygen demand (t-COD) of the manure was reduced when microwave digestion was assisted with peroxide addition. In addition, the volatile fatty acids (VFAs) distribution shifted to simpler chain acids (acetic acid in particular) with an increase in operating temperature. In the second part of the study, digested manure with increased soluble phosphate was tested for the recovery of struvite (magnesium ammonium phosphate) at different pH. It was found that up to 90% of orthophosphate can be removed from the solution. Overall, it was concluded that the oxidizing agent-assisted microwave digestion process can be used upstream of anaerobic digestion, following which the anaerobically digested manure can be used for struvite recovery. Thus, this microwave digestion process presents the potential for enhanced efficiencies in both manure digestion and struvite recovery.     

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.     

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.     

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.     

Effects of acidifying reagents on microwave treatment of dairy manure

Dairy manure, acidified using organic acids (acetic, oxalic, and citric acid) were treated with microwave enhanced advanced oxidation process (MW/H₂O₂-AOP). The effect of a mixture of oxalic acid and commonly used mineral acids (sulfuric and hydrochloric acid) on MW/H₂O₂-AOP was also examined. Substantial amounts of phosphorus were released under MW/H₂O₂-AOP, regardless of organic acid or mineral acid used. All three organic acids were good acidifying reagents; however, only oxalic acid could remove free calcium ion in the solution, and improve settleability of dairy manure. The MW/H₂O₂-AOP and calcium removal process could be combined into a single-stage process, which could release phosphate, solubilize solids and remove calcium from dairy manure at the same time. A mixture of oxalic acid and mineral acid produced the maximum volume of clear supernatant and had an ideal molar ratio of calcium to magnesium for effective struvite (magnesium ammonium phosphate) crystallization process. A single-stage MW/H₂O₂-AOP would simplify the process and reduce mineral acid consumption compared to a two-stage operation. The results of a pilot scale study demonstrate that MW/H₂O₂-AOP is effective in treating manure and recovering resource from dairy farms.     

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。     

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.     

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.     

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。     

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).     

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.     

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.     

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。     

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.     

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。     

A strategy for controlling deposition of struvite in municipal wastewater treatment plants.

This paper presents strategies to reduce the risk of struvite deposition by controlling its location of formation. Two technical routes were investigated: (1) to fix the phosphate into the dewatered sludge cake, and (2) to remove phosphate from centrate or filtrate. Chemicals used include magnesium hydroxide [Mg(OH)2], both of reagent grade and reclaimed from a flue gas desulfurization system, magnesium chloride (MgCl2), calcium hydroxide [Ca(OH)2], ferric chloride (FeCl3) and aluminum sulfate [Al2(SO4)3]. Research results indicate that (1) for anaerobically well-digested sludge, Mg(OH)2 is effective in fixing phosphate into sludge cake and improving sludge dewaterability, and (2) adding Mg(OH)2 into a reactor, located between the sludge dewatering facilities and the centrate or filtrate discharge line, and using air for mixing and carbon dioxide stripping, proves feasible in reducing struvite deposition in centrate or filtrate discharge lines and can generate a potentially valuable plant fertilizer--struvite.     

SBR处理高浓度养猪废水工艺条件

以养猪场废水作为研究对象,采用序列间歇式活性污泥法SBR,通过实验研究了供气量、pH、排泥量、原水稀释倍数、水力停留时间（HRT）对SBR出水水质的影响。结果表明,供气量为375 L/（min·m³）、pH为8.0,并添加排泥100 mL的操作,可使SBR处理效果明显提高,COD、磷和凯氏氮去除率最高分别可达96.37%、94.14%、99.38%。逐步降低进水稀释倍数有利于培养出处理高浓度有机养猪废水的活性污泥,可将平均COD、磷和凯氏氮含量高达9 161.24、33.41和1 502.77 mg/L的养猪废水处理至出水的490.11、5.35和17.84 mg/L。降低HRT对SBR去除率影响不大。     

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。