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。     

Dairy manure treatment, digestion and nutrient recovery as a phosphate fertilizer

A combined approach of biological treatment, solids digestion and nutrient recovery was tested on dairy manure. A sequencing batch reactor (SBR) was operated in three modes, in order to optimize nutrient (nitrogen and phosphorus) removals. The highest average removal efficiencies of 91% for NH4-N, 59% for PO4-P and 80% for total chemical oxygen demand (COD) were achieved. Staining experiments suggested the coexistence of glycogen and phosphorus accumulating organisms. Anaerobic digestion of wasted bio-solids was able to produce a PO4-P concentration of 70 mgL-1 in the supernatant. A pilot-scale experiment, designed to recover phosphorus in the supernatant as struvite (magnesium ammonium phosphate), was able to remove 82% of soluble PO4-P.     

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.     

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。     

Dairy Manure Treatment,Digestion and Nutrient Recovery as a Phosphate Fertilizer

A combined approach of biological treatment, solids digestion and nutrient recovery was tested on dairy manure. A sequencing batch reactor (SBR) was operated in three modes, in order to optimize nutrient (nitrogen and phosphorus) removals. The highest average removal efficiencies of 91% for NH₄-N, 59% for PO₄-P and 80% for total chemical oxygen demand (COD) were achieved. Staining experiments suggested the coexistence of glycogen and phosphorus accumulating organisms. Anaerobic digestion of wasted bio-solids was able to produce a PO₄-P concentration of 70 mgL^?1 in the supernatant. A pilot-scale experiment, designed to recover phosphorus in the supernatant as struvite (magnesium ammonium phosphate), was able to remove 82% of soluble PO₄-P.     

Thermal decomposition of struvite and its phase transition

Intentional crystallization of struvite, before it forms and accumulates on wastewater treatment equipment, solves an important and costly wastewater treatment problem and on the other hand, provides an environmentally sound and renewable nutrient source to the agricultural industry. Struvite was synthesized in the laboratory; it was also produced as pellets in a pilot-scale, fluidized bed reactor, using real centrate resulting from an anaerobic digester. The thermal decomposition of both synthetic struvite and struvite pellets was studied. The decomposition of struvite was found to be dependent on the rate of heating. Through gradual loss of ammonia and water molecules, ultimately struvite was found to be transformed into amorphous magnesium hydrogen phosphate. When struvite was heated in excess water, it was partially transformed into bobierrite, through the gradual loss of ammonia. It was transformed into monohydrate, dittmarite by losing its five water molecules of crystallization, when boiled in excess water.     

工艺条件对鸟粪石法回收磷耗碱量的影响及其理论计算

通过分析磷回收过程中存在的各种耗碱因素,推导出耗碱量的理论计算公式,计算出了不同工艺条件下的理论耗碱量,并与小型连续搅拌反应-沉淀磷回收过程的实验实测值进行比较。结果表明,耗碱量的理论计算值与实验测定值的平均相对误差为13.20%,说明计算方法可用于耗碱量的工程估算;耗碱量随出水pH值的增大而急剧增加,随废水中氨氮含量和磷初始浓度的增加都近似于线性增加,但随镁磷比的增加基本不变。因此,从节约废水处理成本的角度看,磷回收过程中pH值应控制在9.2-9.3,氮磷比控制在3.0-5.0,镁磷比控制在1.1-1.2为佳。磷回收过程的药剂消耗量与废水中磷的浓度和工艺条件有关,以磷初始浓度为124 mg/L,N/Mg/P=5∶1.2∶1,出水pH值为9.20的回收过程为例,处理毎吨废水需消耗片碱0.5313 kg,成本约为1.328元,需消耗氯化镁（含六个结晶水）0.9758 kg,成本约为0.634元。因此,处理每吨废水的药剂成本约为1.962元,其中耗碱约占67.7%。     

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.     

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。     

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.     

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.     

Microwave pretreatment for enhancement of phosphorus release from dairy manure

Both the advanced oxidation process (AOP) using a combination of hydrogen peroxide addition and microwave heating (H2O2/microwave), and the microwave heating process were used for solubilization of phosphorus from liquid dairy manure. About 80% of total phosphate was released into the solution at a microwave heating time of 5 min at 170 degrees C. With an addition of H2O2, more than 81% of total phosphate could be released over a reaction period of 49 h at ambient temperature. The AOP process could achieve up to 85% of total phosphate release at 120 degrees C. The results indicated that both the microwave, and the AOP processes could effectively release phosphate from liquid dairy manure. These processes could serve as pretreatments for phosphorus recovery from animal wastes, and could be combined with the struvite crystallization process to provide a new approach in treating animal wastes.     

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。     

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.     

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.     

Modification of a full-scale sequencing batch reactor operational mode for biological nutrient removal.

Two biological nutrient removal modes, consisting of anaerobic, anoxic, and oxic sequences, were tested in a full-scale sequencing batch reactor. The modes, identified as BNR-S1 and BNR-S2, had average total nitrogen removals of 84 and 89%, respectively, for the months of August to October. Over the same period, total phosphorus removals for BNR-S1 and BNR-S2 were 88 and 87%, respectively. In contrast, total nitrogen and total phosphorus removals for the regular aerobic mode were 54.7 and 44.7%, respectively. When the wastewater temperature changed from approximately 20 to 15 degrees C in the winter months, total nitrogen and total phosphorus removals for BNR-S2 were reduced to 81 and 70%, respectively. Total nitrogen effluent concentrations were between 2.5 and 4 mg-N/L (at approximately 20 degrees C), while the effluent total phosphorus concentrations were between 1 and 2 mg/L. The BNR-S2 mode was found to require less energy per kilogram of soluble chemical oxygen demand removed than the regular and BNR-S1 modes.     

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.     

Laboratory experiments on simultaneous removal of K and P from synthetic and real urine for nutrient recycle by crystallization of magnesium-potassium-phosphate-hexahydrate in a draft tube and baffle reactor

The simultaneous removal of K and P from urine for nutrient recycling by crystallization of magnesium potassium phosphate hexahydrate (MPP) in a laboratory-scale draft tube and baffle reactor (DTBR) is investigated. Results show that mixing speed and hydraulic retention time are important operating factors that influence crystallization and crystal settlement. Slurry should be discharged at a crystal retention time of 11 h to maintain fluidity in the reactor. Further applications of the DTBR using real urine (pretreated by ammonia stripping and diluted five times) showed that 76% K and 68% P were recycled to multi-nutrient products. The crystals collected were characterized and confirmed mainly as a mixture of magnesium ammonium phosphate hexahydrate, MPP, and magnesium sodium phosphate heptahydrate. Results indicate that the DTBR effectively achieved the simultaneous recycling of K and P from urine to multi-nutrient products through MPP crystallization.     

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。