A pilot-scale study of struvite precipitation in a stirred tank reactor: conditions influencing the process

Currently, the two most developed techniques for recovering phosphorus from wastewater consist of the formation of calcium phosphates and struvite (MgNH(4)PO(4).6H(2)O). In this work the influence of the operational conditions on the struvite precipitation process (pH in the reactor, hydraulic retention time, and magnesium:phosphorus, nitrogen:phosphorus, and calcium:magnesium molar ratios) have been studied. Twenty-three experiments with artificial wastewater were performed in a stirred reactor. In order to obtain the pH value maintenance during the crystallization process, a fuzzy logic control has been developed. High phosphorus removal efficiencies were reliably achieved precipitating the struvite as easily dried crystals or as pellets made up of agglomerated crystals.     

Removal of nutrients from piggery wastewater using struvite precipitation and pyrogenation technology

In this paper, removal of nutrients from piggery wastewater by struvite crystallization was conducted using a combined technology of low-cost magnesium source in struvite precipitation and recycling of the struvite pyrolysate in the process. In the present research, it was found that high concentrations of K⁺ and Ca²⁺ present in the solution significantly affected the removal of nutrients. When the struvite crystallization formed at the condition of dosing the magnesite pyrolysate at a Mg:N:P molar ratio of 2.5:1:1, and having a reaction time of 6 h, a majority of nutrients in piggery wastewater can be removed. Surface characterization analysis demonstrated that the main components of the pyrolysate of the obtained struvite were amorphous magnesium sodium phosphate (MgNaPO₄) and MgO. When the struvite pyrolysate was recycled in the process at the pH range of 8.0-8.5, the precipitation effect was optimum. When the struvite pyrolysate was recycled repeatedly at pH 8.5 or without any adjustment of pH, the outcome of the removal of the nutrients in both cases was similar. With the increase in the number of recycle times, the performance of struvite precipitation progressively decreased. An economic evaluation showed that the combination of using low-cost material and recycling of struvite was feasible. Recycling struvite for three process cycles could save the chemical costs by 81% compared to the use of pure chemicals.     

Removal and recovery of phosphorous from swine wastewater by demonstration crystallization reactor and struvite accumulation device

A demonstration crystallization reactor and struvite accumulation device for the removal and recovery of phosphorous was constructed and their performance was evaluated using actual swine wastewater for 3.5 years. The wastewater pH was increased by aeration, and the concentrations of total P and soluble PO(4)-P were reduced by a struvite crystallization reaction induced under a high pH condition. A 30% MgCl(2) addition was effective in enhancing the struvite crystallization reaction. The concentrations of suspended solids, total Zn and total Cu, were also decreased by the settling function of the reactor. On removing the efficiencies of these components, no noticeable seasonal fluctuation in performance was observed during the 3.5-year operation. In terms of maximum yield, 171g struvite was obtained from 1m(3) swine wastewater by the demonstration accumulation device for struvite recovery. The recovered struvite needed only air-drying before use since it was approximately 95% pure even without washing.     

An economic evaluation of phosphorus recovery as struvite from digester supernatant

Phosphorus can be recovered from wastewater through crystallisation of struvite, MgNH(4)PO(4).6H(2)O. Approximately 1 kg of struvite can be crystallised from 100 m(3) of wastewater. Crystallisation is profitable compared to chemical and biological removal of phosphorus due to savings from the reduction in (i) chemicals used for precipitation and sludge disposal; and (ii) downtime for cleaning unwanted struvite formed during chemical and biological removal. The struvite produced annually from a wastewater treatment plant that processed 100 m3/d, would be sufficient to apply on 2.6 ha of arable land, as fertilizer. If struvite were to be recovered from wastewater treatment plants worldwide, 0.63 million tons of phosphorus (as P(2)O(5)) could be harvested annually, reducing phosphate rock mining by 1.6%. Therefore, this technology could provide opportunities to recover phosphorus sustainably from waste streams and preserve phosphorus reserves.     

Application of struvite precipitation as a pretreatment in treating swine wastewater

In this study, the effect of the pretreatment of NH₄-N by struvite precipitation on biological nitrogen removal was investigated in treating swine wastewater. Evaluation was mainly focused on nitrification which occurred in the activated sludge system after struvite precipitation. Laboratory experiments were performed at four different hydraulic retention times (HRT), i.e., 48, 32, 24 and 16 h. Results of the long-term operation of systems showed that the struvite precipitation used as the pretreatment of raw swine wastewater enhanced the nitrification performance in activated sludge system by reducing the applied loading rates of NH₄-N and TCOD in all operating conditions. The reduction of the applied NH₄-N loading rate kept the levels of free ammonia (FA) concentration in biological reactors low and it prevented nitrite accumulation. In addition, the struvite precipitation elicited the biological denitrification reaction and PO₄-P removal by increasing the ratios of carbon-to-nitrogen and carbon-to-phosphorus of wastewater after struvite precipitation. The struvite precipitation also enhanced the biological TCOD removal performance by reducing the toxic effect of FA. Triplicate INT-dehydrogenase tests clearly showed that FA inhibited the degradation of organic matter in activated sludge system. Finally, the struvite precipitation contributed to high TCOD, T-N and PO₄-P removals of 83, 90, and 97% by facilitating biological reaction at a short HRT of 16 h.     

Struvite precipitation in anaerobic swine lagoon liquid: effect of pH and Mg:P ratio and determination of rate constant

Because of increased concern about surface water eutrophication from nutrient-enriched agricultural runoff, many swine producers are encouraged to decrease application rates of waste-based P. Precipitation and subsequent removal of magnesium ammonium phosphate (MgNH(4)PO(4) x 6H(2)O), commonly known as struvite, is a promising mechanism for N and P removal from anaerobic swine lagoon effluent. The objectives of this research were to (i) quantify the effects of adjusting pH and Mg:P ratio on struvite precipitation and (ii) determine the rate constant pH effect for struvite precipitation in anaerobic swine lagoon liquid. Concentrations of PO(4)-P in liquid from two anaerobic swine lagoons were determined after 24 h of equilibration for a pH range of 7.5-9.5 and Mg:P ratios between 1:1 and 1.6:1. Struvite formation reduced the PO(4)-P concentration in the effluents to as low as 2 mgl(-1). Minimum concentrations of PO(4)-P occurred between pH 8.9 and 9.25 at all Mg:P ratios. Struvite precipitation decreased PO(4)-P concentrations by 85% within 20 min at pH 9.0 for an initial Mg:P ratio of 1.2:1. The rate of PO(4)-P decrease was described by a first-order kinetic model, with rate constants of 3.7, 7.9, and 12.3 h(-1) at pH 8.4, 8.7 and 9.0 respectively. Our results indicate that induced struvite formation is a technically feasible method to remove N and P from swine lagoon liquid and it may allow swine producers to recover nutrients for off-farm sale.     

基于好氧反硝化及反硝化聚磷菌强化的低温低碳氮比生活污水生物处理中试研究

【背景】低碳氮比生活污水很难达标处理,多级A/O工艺、生物强化技术及生物膜技术的有机结合可有效解决这一问题。【目的】开发出一种泥膜共生多级A/O工艺并进行中试研究,驯化出高效脱氮除磷菌剂并对系统进行生物强化。【方法】通过测定中试设备出水及污水处理厂出水化学需氧量(Chemical oxygen demand,COD)、氨氮(NH_4~+-N)、硝氮(NO_3~--N)、总氮(Total nitrogen,TN)、总磷(Total phosphorus,TP)对比分析两种工艺的污染物去除效能,利用高通量测序技术对比生物强化技术对系统微生物群落结构的影响。【结果】中试设备对COD、NH_4~+-N、NO_3~--N、TN、TP的去除效果均优于污水处理厂的处理工艺;驯化的低温好氧反硝化菌TN去除率最大值可达84.21%,驯化的低温反硝化聚磷菌群对磷的去除率最高可达85.75%;利用驯化菌群对中试设备进行生物强化后较好地改善了系统NH_4~+-N、NO_3~--N、TN、TP的去除效果;经生物强化后,具有好氧反硝化和反硝化聚磷功能的Pseudomonas菌群明显增多。【结论】泥膜共生多级A/O工艺对于低碳氮比生活污水的处理具有很好的效果,利用生物强化技术可有效提高低温条件下系统污染物去除效能。     

Removal of ammonia as struvite from anaerobic digester effluents and recycling of magnesium and phosphate

A second order kinetic model was developed to predict the rate and extent of NH(4)(+) removal as struvite from anaerobic digester effluents. Alternative to this, NH(4)(+) can be recovered from struvite and the remaining Mg(2+) and PO(4)(3-) can be recycled back to the wastewater to fix more NH(4)(+). The NH(4)(+) solution was retained and the remaining Mg(2+) and PO(4)(3-) were returned back to be mixed with wastewater. In a five-step process, NH(4)(+) recovery was initially 92% and progressively decreased to 77% in the fifth stage, due to loss of Mg(2+) and PO(4)(3-) at each step in the supernatant. Finally, economic analysis of recycling nutrients was performed and compared to the one step process. The cost of NH(4)(+) recovery was calculated as $0.36/kgNH(4)-N which is lower than $7.7/kgNH(4)-N the cost of one step process without considering the market value of struvite obtained in one step process.     

Integrating entrapped mixed microbial cell (EMMC) process for biological removal of carbon and nitrogen from dilute swine wastewater

An entrapped mixed microbial cells (EMMC) process was used to investigate the simultaneous removal of carbon and nitrogen from dilute swine wastewater. Cellulose triacetate was used as the matrix for entrapping the mixed microbial cells. The EMMC process was tested with various oxygen supply conditions (ratios of aeration to non-aeration times) and two types of carrier sizes (large and medium). Also, various pre-treatments with chemical coagulation, screen separation and ammonium crystallization prior to the EMMC process, and post-treatment after the EMMC process were investigated. It was found that at a hydraulic retention time of 30 h and one hour of aeration and one hour of non-aeration, the EMMC process packed with medium carriers after the pretreatment of ammonium crystallization, exhibited the best total nitrogen removal efficiency of 95.1 +/- 1.0% when compared to the other two pre-treatment methods. The total chemical oxygen demand (TCOD) and soluble chemical oxygen demand removal efficiencies were 83.5 +/- 2.2% and 84.1 +/- 1.1%, respectively. Lime post-treatment provided TCOD and total phosphorus removal efficiencies of 59.6 +/- 2.7% and 98.0 +/- 0.5%, respectively. Thus, a cost analysis for ammonium crystallization pre-treatment, EMMC process, and post-treatment with lime was conducted. The unit cost for a 2000 pig operation is approximately dollars 4.91/pig/year. For the application of the EMMC process with the proposed pre- and post-treatments, a suitable farm size needs to be greater than a 2000 pig operation. Because of the high efficiency and the simple operation of simultaneous carbon and nitrogen removal, the EMMC process has the potential for treatment of dilute swine wastewater in a land-limited area and can be manufactured as pre-fabricated wastewater treatment units.     

Recovery of phosphorous from swine wastewater through crystallization

All the phosphate rock Japan needs must be presently imported from abroad because the country has no subterranean phosphorous resources. Therefore, there is a need to accelerate the development of and establish the technologies for phosphorous recovery from waste and wastewater. Swine wastewater has a high potential for phosphorous recovery in Japan. A reactor for removing and recovering phosphorous from swine wastewater was designed with dual functions, crystallization through aeration and separation of formed struvite by settling. However, a dehydration, composting and characterization process was first needed before using sediment sludge, including struvite, on farmland, since the struvite will settle along with huge amounts of other suspended solids (organic matter). For the recovery of pure struvite, an accumulation device was designed and its efficiency examined. The device has a struvite-accumulation face made of stainless steel wire mesh (1 mm in diameter, 1 cm(2) square) to reduce its total weight. During submergence in the aeration column of the demonstration reactor, struvite cross-bridged and accumulated on the face of the device. The struvite could be scraped off easily with only a light brushing, and was found to be approximately 95% pure. Because this device is a very simple structure, it is thought to be acceptable to swine farmers.     

A new method for conservation of nitrogen in aerobic composting processes

Several factors, such as pH, C/N ratio, temperature, mixing and turning, and aeration rate, could affect the loss of ammonia in composting reactions. Substantial loss of ammonia can reduce the nutrient value of the compost product and may lead to a severe odor problem in the composting facility. A new method for conservation of ammonia in composting was proposed and tested in this study. The ammonia being produced during the composting was precipitated into struvite crystals by addition of Mg and P salts. Ammonia volatilization was greatly reduced by this method and it also contributed to a remarkable increase in total ammoniacal-N (TAN) content in the compost, reaching up to 1.4% of dry mass. This value of TAN content was 3-5 times higher than that in normal compost. The scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS) analyses confirmed the formation of struvite crystals in the aerobic composting process.     

Effect of COD/N ratio and salinity on the performance of sequencing batch reactors

The effects of COD/N ratio (3-6) and salt concentration (0.5-2%) on organics and nitrogen removal efficiencies in three bench top sequencing batch reactors (SBRs) with synthetic wastewater and one SBR with fish market wastewater were investigated under different operating schedules. The solids retention time (SRT, 20-100 days) and aeration time (4-10h) was also varied to monitor the performance. For synthetic wastewater, chemical oxygen demand (COD) removal efficiencies were consistently greater than 95%, irrespective of changes in COD/N ratio, aeration time and salt concentrations. Increasing the salt concentrations decreased the nitrification efficiency, while high COD/N ratio's favored better nitrogen removal (>90%). The treatment of real saline wastewater ( approximately 3.2%) from a fish market showed high COD (>80%) and nitrogen (>40%) removal efficiencies despite high loading rate and COD/N fluctuations, which is due to the acclimatization of the biomass within the SBR.     

Plant availability of nutrients recovered as solids from human urine tested in climate chamber on Triticum aestivum L

Recovered nutrients by freezing-thawing from human urine in combination with struvite precipitation and nitrogen adsorption on zeolite and activated carbon have been tested in pot trials with wheat, Triticum aestivum L., in a climate chamber during 21 days. A simple test design using sand as substrate was chosen to give a first, general evaluation of the nutrient (P and N) availability from these sources. Dry weight, plant growth morphology, total-P and total-N were analysed. The tests show a slow-release of nutrients (P and N) from struvite and from N-adsorbents. The nitrogen in all treatments was in the deficiency range for optimum yield for wheat. Higher pH than usual for soil tests contributed to the difficulties in plant uptake, especially in the pots with only struvite (with highest MgO addition) as nutrient source.     

Ammonia removal from anaerobically digested dairy manure by struvite precipitation

Ammonia is one of the most important contaminants impairing the quality of water resources. When this is considered along with the fact that the global demand for nitrogenous fertilizers is in constant rise, the need for recovery as well as removal of nitrogen is well justified. Crystallization of N and P in the form of struvite (MgNH₄PO₄·6H₂O), which is a slow releasing and valuable fertilizer, is one possible technique for this purpose. This study investigated the removal of NH₄⁺ through struvite precipitation from the effluents of one- (R1) and two-phase (R2) anaerobic reactors digesting dairy manure. To force the formation of struvite in the anaerobic reactor effluents, Mg²⁺ ion was added by using both Mg(OH)₂ and MgCl₂·6H₂O. To prevent the effect of different total phosphorus (TP) concentration in the effluents of R1 and R2, as well as to not limit the formation of struvite, an excess amount of PO₄³⁻ (0.14 M) was added in the form of Na₂HPO₄. Different stoichiometric Mg²⁺:NH₄⁺:PO₄³⁻ ratios were tested to determine the required Mg²⁺ concentrations for maximum NH₄⁺ removal by keeping NH₄⁺:PO₄³⁻ ratio constant for the effluents of reactors R1 and R2. The results revealed that very high NH₄⁺ removal efficiencies (above 95%) were possible by adding Mg²⁺ ions higher than 0.06 M concentration in the effluents from reactors R1 and R2. It was also observed that the initial pH adjustment to 8.50 using NaOH did not result in any significant increase in the removal of NH₄⁺ and the removal of NH₄⁺ in the reactors treated with MgCl₂·6H₂O was higher than those treated with Mg(OH)₂ for the same Mg²⁺ concentration.     

Sewage sludge management for phosphorus recovery as struvite in EBPR wastewater treatment plants

The influence of separate and mixed thickening of primary and secondary sludge on struvite recovery was studied. Phosphorus precipitation in the digester was reduced from 13.7 g of phosphorus per kg of treated sludge in the separate thickening experiment to 5.9 in the mixed thickening experiment. This lessening of the uncontrolled precipitation means a reduction of the operational problems and enhances the phosphorus availability for its later crystallization. High phosphorus precipitation and recovery efficiencies were achieved in both crystallization experiments. However, mixed thickening configuration showed a lower percentage of phosphorus precipitated as struvite due to the presence of high calcium concentrations. In spite of this low percentage, the global phosphorus mass balance showed that mixed thickening experiment produces a higher phosphorus recovery as struvite per kg of treated sludge (i.e., 3.6 gP/kg sludge vs. 2.5 gP/kg sludge in separate thickening).     

Biotransformation of struvite by Aspergillus niger: phosphate release and magnesium biomineralization as glushinskite

Struvite (magnesium ammonium phosphate-MgNH₄PO₄·6H₂O), which can extensively crystallize in wastewater treatments, is a potential source of N and P as fertilizer, as well as a means of P conservation. However, little is known of microbial interactions with struvite which would result in element release. In this work, the geoactive fungus Aspergillus niger was investigated for struvite transformation on solid and in liquid media. Aspergillus niger was capable of solubilizing natural (fragments and powder) and synthetic struvite when incorporated into solid medium, with accompanying acidification of the media, and extensive precipitation of magnesium oxalate dihydrate (glushinskite, Mg(C₂O₄).2H₂O) occurring under growing colonies. In liquid media, A. niger was able to solubilize natural and synthetic struvite releasing mobile phosphate (PO₄³⁻) and magnesium (Mg²⁺), the latter reacting with excreted oxalate resulting in precipitation of magnesium oxalate dihydrate which also accumulated within the mycelial pellets. Struvite was also found to influence the morphology of A. niger mycelial pellets. These findings contribute further understanding of struvite solubilization, element release and secondary oxalate formation, relevant to the biogeochemical cycling of phosphate minerals, and further directions utilizing these mechanisms in environmental biotechnologies such as element biorecovery and biofertilizer applications.     

Nutrient recovery from domestic wastewater using a UASB-duckweed ponds system

The pilot-scale wastewater treatment system used in this study comprised a 40-l UASB reactor (6-h HRT) followed by three duckweed ponds in series (total HRT 15 days). During the warm season, the treatment system achieved removal values of 93%, 96% and 91% for COD, BOD and TSS, respectively. Residual values of ammonia, TKN and total phosphorus were 0.41 mg N/l, 4.4 mg N/l and 1.11 mg P/l, with removal efficiencies of 98%, 85% and 78%, respectively. The system achieved 99.998% faecal coliform removal during the warm season with final effluent containing 4 x 10(3) cfu/100 ml. During the winter, the system was efficient in removing COD, BOD and TSS but not nutrients. The system was deficient in the removal of faecal coliforms during the winter, producing effluent with 4.7 x 10(5) cfu/100 ml. During the warm season, the N removal consisted of 80% by plant uptake, 5% by sedimentation and 15% unaccounted for. A duckweed production rate of 33 t dry matter per hectare per 8 months was achieved.     

Influence of wastewater composition on nitrogen and phosphorus removal and process control in A2O process

A bench-scale anaerobic–anoxic–oxic (A²O) bioreactor with steady denitrifying phosphorus removal performance was tested to determine the influence of influent C/N ratio (SCOD/TN) and C/P ratio (SCOD/TP) on biological nutrient removal for treating synthetic brewage wastewater; meanwhile, the spatial profiles of DO, pH and ORP sensors in such systems were investigated. The results showed that influent C/N ratio had significant effect on the TN, TP removal efficiencies and the ratio of anoxic to aerobic P uptake amount. The maximal TN and TP removal efficiencies could be achieved when influent C/N ratio was kept at about 7.1 and 5, respectively. Besides, the ratio of anoxic to aerobic P uptake amount was found to be linearly dependent on the influent C/N ratio with coefficient R ² of 0.685 when total recirculation ratio was constant at 3.5. Influent C/P ratio had an important effect on the TP removal efficiency, while it hardly affected TN removal efficiency. In addition, the TP removal efficiency reached the maximum for influent C/P ratio of 42. On the other hand, it was also found that the typical profiles of DO, pH and ORP sensors could be observed, and they have similar trends at the different influent C/N ratio and C/P ratio. It was suggested that the operational state could be well known according to the changes of simple on-line sensors.     

Assessing the feasibility of achieving biological nutrient removal from wastewater at an Irish food processing factory

In Ireland, wastewaters emanating from the food industry typically contain elevated levels of nitrogen and phosphorus before treatment. Two pilot scale studies were performed to determine the feasibility of achieving biological N and P removal on-site at a food ingredients plant. The wastewater treated by the pilot reactors was that which resulted from the day-to-day production in the full-scale food ingredients plant. Both reactors were of the anaerobic/anoxic/oxic (A/A/O) design, however the sizing of the zones was varied in this study. In the first pilot study, while treating a wastewater of the following strength: 1008 mg COD/l; 30.1 mg NH4-N/l and 26.7 mg P/l, removal efficiencies of 93%, 99% and 98% were obtained for COD, NH4-N and P, respectively. In the second study, while operating at reduced hydraulic retention times and lower recycle rates, the pilot plant treated a wastewater of the following strength: 1757 mg COD/l; 62 mg NH4-N/l and 57 mg P/l, with removal efficiencies of 94%, 97% and 75% obtained for COD, NH4-N and P, respectively. This work showed that biological nutrient removal could be successfully applied to treatment of food industry wastewaters.     

Partial nitrifying granule stimulated by struvite carrier in treating pharmaceutical wastewater

Aerobic granule was successfully cultivated in SBR (sequencing batch reactor) by struvite carrier (magnesium ammonium phosphate, MgNH₄PO₄), which can increase polysaccharides to 42.2 mg/gMLVSS (mixed liquor volatile suspended solid) versus only 28.4 mg/gMLVSS of the sludge without it. Meanwhile, it was found that struvite play a positive role in initial granulation and bacterial group distribution in treating pharmaceutical wastewater, involving effect of solid surface and special contents of struvite. The results of fluorescence in situ hybridization technique indicate that ammonia-oxidizing bacteria can dominate over nitrite-oxidizing bacteria in mature granules. COD removal efficiency of 90 % and NO₂ ^?–N:(NO₂ ^?–N?+?NO₃ ^?–N) accumulation efficiency of 89 % were achieved in stable state. Emphasis is placed on that struvite addition can be applied as a new-type carrier to promote formation of partial nitrification granular sludge.