Struvite recovery from anaerobically digested dairy manure: A review of application potential and hindrances.

Anaerobically digested dairy manure is rich in ammonium, orthophosphates, and magnesium, indicating a high potential for struvite recovery. Continuous generation of large amounts of dairy manure plus increasing global interest in anaerobic digestion of dairy manure suggest a huge market for struvite production with anaerobically digested dairy manure. However, the complex chemical composition of digested dairy manure presents hindrances to struvite recovery. This review paper assesses the significance and potential of struvite recovery from anaerobically digested dairy manure, identifies the factors hindering struvite recovery, and discusses the methods to overcome hindrances and the measures to improve phosphorus speciation of dairy manure for struvite formation. This paper proposes using "struvite recovery potential" or Pstruvite based on the least molar activity of struvite component ions in addition to "supersaturation ratio" to identify the potential for struvite recovery. The probable hindrances mainly include high Ca(2+) concentration and molar activity ratios of Ca(2+): Mg(2+) and Ca(2+): PO4(3-), high ionic strength, and high alkalinity. Struvite formation and purity is likely a function of all the interfering variables, rather than just a single factor with digested dairy manure. Potential enhancement measures need to be tested for technical and economic feasibility and applicability to various sources of digested dairy manure. This review paper provides guidance to overcoming the hindrances of digested dairy manure to struvite formation.

Effect of magnesium dose on amount of pharmaceuticals in struvite recovered from urine.

Phosphorus (P) recovery was carried out through struvite precipitation from urines. Human urine, however, contains not only high nutrients for plants, such as P and nitrogen, but also pharmaceuticals and hormones. In this work, effects of magnesium (Mg) dose (in terms of Mg:P ratio) on P recovery efficiency and pharmaceutical amounts contained in struvite were investigated. Batch-scale experiments of synthetic and human urines revealed that struvite precipitation formed more X-shaped crystals with an increased molar ratio of Mg:P, while the amount of pharmaceuticals (tetracycline, demeclocycline, and oxytetracycline) in struvite decreased with an increased molar ratio of Mg:P. The lowest pharmaceutical amounts in struvite were found at the Mg:P ratio of 2:1 from both samples. Moreover, the maximum P recovery efficiency, quantity and purity of struvite were found in the range of 1.21 to 2:1. It indicated that the molar ratio of Mg:P has a significant impact on struvite precipitation in terms of pharmaceutical amounts in struvite; morphology, quantity and purity of struvite; and P recovery.

A new algorithm for design, operation and cost assessment of struvite (MgNH4PO4) precipitation processes.

Deliberate struvite (MgNH4PO4) precipitation from wastewater streams has been the topic of extensive research in the last two decades and is expected to gather worldwide momentum in the near future as a P-reuse technique. A wide range of operational alternatives has been reported for struvite precipitation, including the application of various Mg(II) sources, two pH elevation techniques and several Mg:P ratios and pH values. The choice of each operational parameter within the struvite precipitation process affects process efficiency, the overall cost and also the choice of other operational parameters. Thus, a comprehensive simulation program that takes all these parameters into account is essential for process design. This paper introduces a systematic decision-supporting tool which accepts a wide range of possible operational parameters, including unconventional Mg(II) sources (i.e. seawater and seawater nanofiltration brines). The study is supplied with a free-of-charge computerized tool (http://tx.technion.ac.il/~agrengn/agr/Struvite_Program.zip) which links two computer platforms (Python and PHREEQC) for executing thermodynamic calculations according to predefined kinetic considerations. The model can be (inter alia) used for optimizing the struvite-fluidized bed reactor process operation with respect to P removal efficiency, struvite purity and economic feasibility of the chosen alternative. The paper describes the algorithm and its underlying assumptions, and shows results (i.e. effluent water quality, cost breakdown and P removal efficiency) of several case studies consisting of typical wastewaters treated at various operational conditions.

Recovery of struvite via coagulation and flocculation using natural compounds.

One of the major setbacks of struvite recovery processes is the difficulty in harvesting struvite crystals. This study evaluates the use of different coagulants to improve precipitation of struvite (MgNH4PO4.6H20) crystals. Chitosan and poly(diallyldimethyl ammonium chloride) (Poly-DADMAC) as a coagulant-flocculent and alginate and bentonite as a coagulant aid have been examined in jar tests. Also, a continuous three-phase process, i.e., struvite crystallization, coagulation/flocculation and precipitation process, was set up for real wastewater. Addition of chitosan as the coagulant and bentonite as the coagulant aid was significantly more efficient in forming struvite flocs in comparison to Poly-DADMAC alone or with coagulant aid, which did not show any positive effect. The calculated average settling velocity of struvite with chitosan-bentonite addition in synthetic and in real wastewater increased by approximately 5.3 and 2.8 folds, respectively, compared with that of no coagulant/flocculent addition. Phosphorus recovery of over 70% was achieved by the continuous process. Findings in this study clearly confirmed the possibility of using chitosan and bentonite as an efficient coagulant-flocculent to enhance the recovery of struvite crystals.

Enhanced struvite recovery from wastewater using a novel cone-inserted fluidized bed reactor.

The feasibility of struvite recovery at low (12.5 mg/L) and high (120 mg/L) phosphorus concentrations was studied by constructing a novel fluidized bed reactor with cones (FBRwc) and without cones (FBRwoc). The crystallization process was continuously operated for 133 days under different hydraulic retention times (HRT = 1-10 hr), pH (7.5-10), and molar ratios of Mg/P (0.75-1.75), N/P (1-10) and Ca/Mg (0-2). The optimum operating conditions of HRT, pH, Mg/P and N/P molar ratios were found to be 2 hr, 9, 1.25, and 7.5, respectively. Under these optimum conditions, the phosphorus precipitation efficiencies of FBRwc were 93% for low and 98% for high phosphorus influent; however, the efficiencies were 78% and 81% for FBRwoc, respectively. Due to crystal losses at each junction (17%-31%), the crystal recovery efficiency of FBRwoc was relatively low (47%-65%) for both influent concentrations. However, the losses were minimal in FBRwc, which showed 75% and 92% crystal recovery for low and high phosphorus concentrations, respectively. At low calcium concentration, crystal chemical analysis showed the product to be pure struvite (> 99%). The scanning electron microscope and X-ray diffraction results further confirmed that the crystal recovered from FBRwc contained pure struvite, which could be considered a high quality fertilizer. Except HRT, all parameters (pH, Mg/P, N/P and Ca/Mg) were found to be influencing factors for FBRwc performance. Overall, inserting cones in each part of the reactor played a significant role in enhancing struvite recovery from a wide range of phosphorus-containing wastewater.

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.

Recovery of phosphorus as struvite from sewage sludge ash.

Phosphorus (P) is an element vital for all living organisms, yet the world's reserves of phosphate rock are becoming depleted. This study investigated an effective P recovery method from sludge ash via struvite precipitation. Results showed that more than 95% of the total P content was extracted from sludge ash by applying 0.5 mol/L HCl at a liquid/solid ratio of 50 mL/g. Although heavy metal leaching also occurred during P extraction, cation exchange resin efficiently removed the heavy metals from the P-rich solution. Orthogonal tests showed that the optimal parameters for P precipitation as struvite would be a Mg:N:P molar ratio of 1.6:1.6:1 at pH 10.0. X-ray diffraction analysis validated the formation of struvite. Further investigations revealed that the harvested precipitate had a high struvite content (97%), high P bioavailability (94%), and low heavy metal content, which could be considered a high quality fertilizer.

Phosphorus removal from anaerobically digested swine wastewater through struvite precipitation.

Phosphorus removal from agricultural wastewater streams is an important aspect of managing surface water quality, due to the contribution of phosphorus to eutrophication. Removal of phosphorus through struvite precipitation allows for its recovery as a potential fertilizer, and by determining the best conditions for struvite precipitation the removal process can be optimized. The effects of pH, Mg:P ratio, and time on struvite precipitation from anaerobically digested swine manure effluent were investigated. Effluent with Mg:P ratios from 1.0:1 to 1.6:1 were adjusted to pH values between 7.5 and 9.5 and left to equilibrate for 24 h. Results indicate that phosphorus removal increased with increasing pH and Mg:P ratio; the maximum phosphorus removal achieved was 80% at pH 9.0 and a Mg:P ratio of 1.6:1. The purest struvite precipitate was found at pH 7.5, with calcium carbonate and struvite precipitating at higher pH values. A continuously stirred batch of centrate was adjusted to pH 8.4 to determine the struvite formation rate constant. The rate constant was found to be 1.55 h(-1), with 17% phosphorus removal during the first 20 min. The results indicate that struvite precipitation could be a viable method of phosphorus removal from anaerobically digested swine manure.

Selective separation of phosphate and fluoride from semiconductor wastewater.

Hydrofluoric acid (HF) and phosphoric acid (H(3)PO(4)) are widely used in semiconductor industry for etching and rinsing purposes. Consequently, significant amount of wastewater containing phosphate and fluoride is generated. Selective separation of phosphate and fluoride from the semiconductor wastewater, containing 936 mg/L of fluoride, 118 mg/L of phosphate, 640 mg/L of sulfate, and 26.7 mg/L of ammonia, was studied. Chemical precipitation and flotation reactions were utilized in the two-stage treatment processes. The first-stage reaction involved the addition of magnesium chloride (MgCl(2)) to induce selective precipitation of magnesium phosphate. The optimal condition was pH 10 and molar ratio, [Mg(2 + )]/[(PO(4) (3-))], of 3:1, and 66.2% of phosphate was removed and recovered as bobierrite (Mg(3)(PO(4))(2).8H(2)O). No reaction was found between MgCl(2) and fluoride. Calcium chloride (CaCl(2)) was used in the second-stage reaction to induce precipitation of calcium fluoride and calcium phosphate. The optimum molar ratio, [Ca(2 + )]/[F(-)], was 0.7 at pH 10, and residual fluoride concentration of 10.7 mg/L and phosphate concentration of lower than 0.5 mg/L was obtained. Thermodynamic equilibrium was modeled with PHREEQC and compared with experimental results. Sodium dodecylsulfate (SDS) was an effective collector for subsequent solid-liquid removal via dispersed air flotation (DiAF). The study demonstrated that phosphate can be selectively recovered from the wastewater. Potential benefits include recovery of phosphate for reuse, lower required dosage of calcium for fluoride removal, and less amount of CaF(2) sludge.

Application of struvite precipitation coupled with biological treatment to slaughterhouse wastewaters.

In this study, struvite precipitation coupled with an activated sludge process was applied to slaughterhouse wastewaters. Biological treatability characteristics of the wastewater were evaluated in a wide organic loading range of 0.06-0.42 g COD (g MLVSS)(-1)d(-1) to assess COD removal as well as the extent of nitrification. Results of biological treatment of raw wastewater indicated that COD removal varied between 88% and 99% and complete nitrification was achieved at 0.1 g COD (g MLVSS)(-1)d(-1) and lower organic loadings. Biological treatment of the struvite-precipitated sample, which required no nitrification, yielded 86% COD removal at the organic removal of 0.3 g COD (g MLVSS)(-1)d(-1). Struvite precipitation of both raw and biologically treated wastewater was at effective stoichiometric magnesium and phosphate doses to ammonia and between pH values of 9.0 and 9.5, providing ammonia concentrations of 20-30 mg N L(-1) in the effluent and being independent of initial concentrations. The application of struvite precipitation both prior to and after biological treatment resulted in similar effluent qualities and provided the additional benefit of having a high-rate activated sludge system instead of a low organic loading system with nitrification-denitrification. An additional benefit of struvite precipitation was the production of sludge which had recovery potential as a fertilizer. Among the tested treatment schemes, biological treatment following struvite precipitation seemed to be more advantageous in terms of process stability.

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).

Assessing struvite precipitation in a pilot-scale fluidized bed crystallizer.

The recovery of phosphates from biological wastewater treatment plants, through struvite crystallization, minimizes operational downtime and offers the potential for cost-effective recovery. The pilot-scale, fluidized bed reactor developed at the University of British Columbia (UBC) was found to be effective in recovering phosphate in the form of nearly pure struvite product, from an anaerobic digester centrate. The desired degree of phosphate removal was achieved by maintaining operating pH 8.0-8.2, and recycle ratio 5-9, to control the supersaturation conditions inside the reactor. The performance of the system was found to be optimal when the in-reactor supersaturation ratio was 2-6. In-reactor magnesium to phosphate molar ratio was found to be an important parameter to maintain system performance. In-reactor ammonium to phosphate molar ratio was also found to maintain a good correlation with phosphate removal. The influence of organic ligands on the struvite precipitation was investigated for a small molecular weight organic ligand, acetate, using a chemical equilibrium model PHREEQC. An acetate concentration below about 100 mg l(-1) was not found to affect the precipitation potential of struvite. Calcium and carbonate ion did not have any noticeable effect in struvite crystallization of struvite, under the operational concentrations utilized. Since the precipitation of calcium and carbonate compounds was controlled by kinetic factors, rather than thermodynamic solubility alone, the solid precipitates harvested were pure struvite, with undetectable impurities.

Beneficial phosphate recovery from reverse osmosis (RO) concentrate of an integrated membrane system using polymeric ligand exchanger (PLE).

Phosphorus (P) discharge to surface water is a major environmental problem. Wastewater treatment is targeted towards removal of this nutrient to prevent degradation of surface water. Integrated membrane systems (IMS) are increasingly being considered for wastewater reclamation, and provide excellent removal of P compounds. However, reverse osmosis (RO), which forms an integral part of these IMSs, concentrates most dissolved substances including P-species such as phosphates in the RO waste stream. In this study, removal of phosphate from this stream using polymeric ligand exchange (PLE) resins was investigated. Further, the possibility of phosphate recovery through struvite (MgNH(4)PO(4).6H(2)O) precipitation was tested. Struvite has been promoted as a slow release fertilizer in recent years. This study demonstrates that PLEs can be successfully used to remove phosphate from RO-concentrate, and to recover more than 85% of the adsorbed phosphorus from the exhausted media and precipitated as a beneficial product (struvite). The approach, presented in this study, suggests advantages of providing economic benefit from a waste product (RO) while avoiding phosphorus discharge to the environment.

Recovery of nitrogen and phosphorous as struvite from swine waste biogas digester effluent.

OBJECTIVE: To investigate the feasibility of nitrogen and phosphorus recovery from swine waste biogas digester effluent and the effects of pH and NH4+: Mg2+: PO4(3-) molar ratio on its precipitation. METHODS: Precipitation experiments with swine waste biogas digester effluent were conducted at pH 7.5, 8.0, 8.5, and 9.0 together with NH4+: Mg2+: PO4(3-) molar ratios 1: 0.2: 0.08, 1: 1: 1, and 1: 1.5: 1.5. Chemical and X-ray diffraction (XRD) analysis were done to determine the composition of the precipitate. RESULTS: The highest removal and recovery of NH4+ and PO4(3-) were achieved at pH 9.0 in each experiment. The elevation of pH to 9.0 alone could decrease the initial PO4(3-) concentration from 42 mg L(-1) to 4.7 mg L(-1) and 89.2% PO4(3-) recovery was achieved. The pH-molar ratio combination 9.0-1: 1.5: 1.5 effected 76.5% NH4+ and 68.5% PO4(3-) recovery. The molar ratio of 1: 1: 1 together with pH elevation to 9.0 was determined to be the optimum combination for both NH4+ and PO4(3-) removal as it recovered over 70% and 97% of the initial NH4+ and PO4(3-), respectively. CONCLUSIONS: Nitrogen and phosphorus can be recovered from biogas digester effluent as struvite.

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.

Determination of magnesium in foods by single-sweep polarography.

In KOH, the Mg(II)-bromopyrogallol red (BPR) complex produced a very sensitive polarographic wave at -1.30 V. The wave height was linear with the concentration of Mg(II) in the range of 0.05 to 2 microg/mL. The detection limit was 0.01 microg/mL. The electrochemical behavior of Mg(II)-BPR was studied by electrochemical and spectrophotometric methods. Experiments proved that the polarographic wave of Mg(II)-BPR was due to the reduction of BPR in the Mg(II)-BPR complex. The method, which was sensitive, selective, and simple to perform, was used to determine magnesium in foods, and the results were consistent with those obtained by atomic absorption spectroscopy.

Model-based evaluation of struvite recovery from an in-line stripper in a BNR process (BCFS).

Phosphate removal and recovery can be combined in BNR processes. This may be realised by struvite precipitation from the supernatant of the sludge in anaerobic compartments. This can be beneficial for either improving bio-P removal effluent quality or lowering the influent COD/P ratio required for bio-P removal. For this reason, a patented BNR process, BCFS, was developed and applied in The Netherlands. Several questions relating to P-recovery and behaviour of the system remain unclear and need to be ascertained. For this purpose, a modelling technique was employed in this study. With the help of a previous developed model describing carbon oxidation and nutrient removal, three cases were fully simulated. The simulations demonstrated that there was an optimal stripping flow rate and P-recovery would increase in costs and bio-P activity might be negatively affected due to decreased bio-P efficiency if this value was exceeded. The simulations indicated that the minimal COD(biod)/P ratio required for the effluent standard (1 g P/m3) could be lowered from 20 to 10 with 36% of P-recovery. A simulation with dynamic inflow revealed that the dynamic influent loads affected slightly the anaerobic supernatant phosphate concentration but the effluent phosphate concentration would not be affected with regular P-recovery.

Isolation and Physical Property Optimization of an Amorphous Drug Substance Utilizing a High Surface Area Magnesium Aluminometasilicate (Neusilin(®) US2).

Control and optimization of the physical properties of a drug substance (DS) are critical to the development of robust drug product manufacturing processes and performance. A lack of isolatable, for example, crystalline, DS solid forms can present challenges to achieving this control. In this study, an isolation scheme for an amorphous DS was developed and integrated into the synthetic route producing DS with optimized properties. An inert absorbent excipient (Neusilin® US2) was used to isolate the DS via a novel antisolvent scheme as the final step of the route. Isolation was executed at kilogram scale utilizing conventional equipment. The resulting 50 wt% DS:Neusilin complex had improved physical stability and exceptional micromeritic and tableting properties. Improved dissolution was observed and attributed to enhanced dispersion and increased surface area. Characterization data suggest a high degree of penetration of the DS into the Neusilin, with DS occupying 70% of mesopore and 12% of macropore volume. This approach has application in the isolation and particle engineering of difficult to isolate DS without additional unit operation, such as spray drying, and has the potential for a high degree of optimization and control of physical properties over the course of DS development.

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.

Epidemiology of canine urolithiasis in the Czech Republic from 1997 to 2002.

OBJECTIVES: To compare data on the epidemiology of canine urolithiasis in the Czech Republic with that from other countries. METHODS: The records from the Centre for Mineralogical Analysis from 1997 to 2002 were reviewed. The data were obtained from mineralogical analysis of 1366 canine uroliths obtained from patients in the Czech Republic. These included 396 females and 629 males. RESULTS: Sixty-eight breeds plus crossbreeds were identified. Eight breeds plus the crossbreeds accounted for 71.3 per cent of all cases. Males were affected more frequently than females (61.4 per cent versus 38.6 per cent). Struvites significantly predominated in females, while in males calcium oxalates, brushites and cystines were the most common stones. Most of the uroliths (48.9 per cent) were 5 mm or less in dimension. By 2001, struvite was the most frequent (38.5 to 44.1 per cent) urolith, followed by calcium oxalate (26.5 to 32.0 per cent). In 2002, calcium oxalate became the most frequent calculus, followed by struvite, mixed calculi and others. CLINICAL SIGNIFICANCE: Comparison of these results with studies by other authors showed that for most of the monitored parameters there was agreement with respect to the proportions of different breeds within the populations of dogs in different geographical areas.