Predicting struvite formation for phosphorus recovery from human urine using an equilibrium model.

Interest in phosphorus recovery from urine diverted from faeces has been growing recently. Phosphorus in urine can be precipitated out as struvite (MgNH4PO4 x 6H2O) with addition of magnesium salt under alkaline conditions. Struvite formation, however, should be more well understood for its practical application. We predicted the struvite formation with a development of a new equilibrium model. The model considered the formation of eight different kinds of precipitates, including struvite, with effects of ionic strength and temperature. In addition, experiments on struvite formation in urine were conducted for the model validation. The model prediction of struvite formation had good agreement with the experimental results. The optimum pH to form struvite was predicted to be 9.4-9.7. In order to precipitate 99% of phosphate in urine with 1.5 fold Mg concentration to PO4-P, the pH value was necessary to be more than 8.1 based on the model prediction.     

Recovering phosphorus as struvite from the digested swine wastewater with bittern as a magnesium source

Recovering nitrogen and phosphorus through struvite (MgNH4PO4 6H2O) crystallization from swine wastewater has gained increasing interest. However, swine wastewater contains complex compositions, which may hinder the formation of struvite crystal and affect the purity of the precipitates by forming other insoluble minerals. In this work, experiments were carried out to evaluate struvite precipitation in the anaerobically digested swine wastewater, with dosing bittern as a low-cost magnesium source. Exceeded 90% phosphate removal and 23-29% ammonium reduction were obtained. FTIR, XRD and mass balance analysis were combined to analyze the species of precipitated minerals. Results showed that the precipitates were struvite, mixed with amorphous calcium phosphate (ACP) and brucite. The presence of Ca2+ diminished the percentage of struvite and gave rise to ACP formation. Controlling pH below 9.5 and bittern dosage above 1% (w/w) could inhibit ACP precipitation and harvest a highly pure struvite crystal product.     

Recovery oriented phosphorus adsorption process in decentralized advanced Johkasou

Decentralized advanced wastewater treatment using adsorption and desorption process for recovery and recycling oriented phosphorus removal was developed. Adsorbent particles made of zirconium were set in a column, and it was installed as subsequent stage of BOD and nitrogen removal type Johkasou, a household domestic wastewater treatment facility. The water quality of the effluent of adsorption column in a number of experimental sites was monitored. The effluent phosphorus concentration was kept below 1 mg l(-1) during 90 days at all the sites. Furthermore, over 80% of the sites achieved 1 mg l(-1) of T-P during 200 days. This adsorbent was durable, and deterioration of the particles was not observed over a long duration. The adsorbent collected from each site was immersed in alkali solution to desorb phosphorus. Then the adsorbent was reactivated by soaking in acid solution. The reactivated adsorbent was reused and showed almost the same phosphorus adsorption capacity as a new one. Meanwhile, the desorbed phosphorus was recovered with high purity as trisodium phosphate by crystallization. It is proposed as a new decentralized system for recycling phosphorus that paves the way to high-purity recovery of finite phosphorus.     

Effects of organic and inorganic acids on phosphorus release from municipal sludge.

This paper reports on the effects of inorganic acids (sulphuric acid, hydrochloric acid, nitric acid) and organic acids (citric acid, oxalic acids) for phosphorus recovery from sludge and struvite precipitation results. It was observed that both inorganic acid and organic acids were effective at phosphorus release. The studies on precipitation of released phosphorus from sludge as magnesium ammonium phosphate (struvite) were also done using nitric and oxalic acids. Phosphorus and heavy metals of leachate were analyzed before and after precipitation. It was observed that heavy metal concentrations in the extracted samples decrease after precipitation. Precipitation was accomplished by using extract derived with nitric acid; however, in oxalic acid applications, it was not achieved. When the chemical constituents of the dried material were examined oxygen, sodium and nitrogen were found to be the major elements.     

Phosphorus recovery from wastewater through struvite formation in fluidized bed reactors: a sustainable approach.

Recovery of phosphate as struvite (MgNH4PO4.6H2O), before it forms and accumulates on wastewater treatment equipment, solves wastewater treatment problems and also provides environmentally sustainable, renewable nutrient source for the agriculture sector. A pilot-scale fluidized bed reactor was used to recover phosphate through crystallization of struvite, from anaerobic digester centrate at the Lulu Island Wastewater Treatment Plant, Richmond, British Columbia, Canada. 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 in-reactor supersaturation ratio was 2-6. Among several other operating parameters, apparent upflow velocity and magnesium to phosphate molar ratio were also found important to maintain system performance, both in terms of efficiency of phosphate removal and recovery as struvite pellets. A narrow window of upflow velocity (400-410 cm/min) was found to be effective in removing 75-85% phosphate. TOC level inside the rector was found to affect the performance to some extent. The precipitation potential of struvite could be successfully predicted using a thermodynamic solubility product value of 10(-13.36) and its temperature dependence in PHREEQC.     

污水处理领域磷回收技术及其应用

介绍了国内外从污水中磷回收研究与应用现状,多以含磷丰富的污泥脱水上清液、厌氧污泥消化液以及富磷废水为磷源,鸟粪石、磷酸钙等沉淀是目前广泛采用的回收形式。简述污水处理领域的磷回收技术有沉淀法,结晶法,电渗析法、离子交换等。沉淀法中鸟粪石、磷酸钙等的研究相对较为成熟,应用较多。最后展望了我国污水处理领域磷回收前景,2005年我国污水中的磷量相当于2000年全国磷矿开采量的42.7%,具有广泛的回收前景和环境经济效益。     

Extraction efficiency of phosphate from pre-coagulated sludge with NaHS.

The recovery of phosphorus from sewage and sludge treatment systems is particularly important because it is a limited resource and a large proportion of the phosphorus currently used in Japan must be imported. We have been experimentally evaluating recovery methods with sulphide. In this study, we focussed on the extraction of phosphate from the sludge, and sought to achieve a greater extraction efficiency and to validate the extraction mechanism. We conducted three experiments, i.e. a sludge-type experiment, a coagulant ratio of pre-coagulated sludge experiment, and a concentration of pre-coagulated sludge experiment. Phosphate was extracted not with normal sewage sludge but with pre-coagulated sludge and FePO4 reagent at S/Fe = 1.0-2.0. A coagulant ratio of 23mg Fe L(-1) was required in the precoagulation process to effectively extract phosphate. A high concentration of pre-coagulated sludge was required for the phosphate extraction. The mass balance was calculated, and 44.0% of phosphorus was extracted to supernatant, and 98.5% of iron and 98.3% of sulphur (44.1% of sulphur was sulphide). Thus, phosphate can be selectively separated from iron by the phosphate extraction method with NaHS, and phosphorus and iron can be recovered and reused at sewage treatment plants using ferric chloride as a coagulant.     

A study of NH3-N and P refixation by struvite formation in hybrid anaerobic reactor.

This research is concerned with the removal of ammonia nitrogen and phosphorus in foodwaste by crystallization. Reductions have been achieved by struvite formation after the addition of magnesium ions (Mg2+). Magnesium ions used in this study were from magnesium salts of MgCl2. The results of our analysis using scanning electron microscopy and energy dispersive X-ray analysis showed that the amount of struvite in precipitated sludge grew enough to be seen with the naked eye (600-700 microm). EDX analysis also showed that the main components of the struvite were magnesium and phosphorus. NH3-N removal efficiency using MgCl2 was 67% while PO4-P removal efficiency was 73%. It was confirmed that nitrogen and phosphorus could be stabilized and removal simultaneously through anaerobic digestion by Mg, NH3 and PO4-P, which were necessary for struvite formation.     

Energy and phosphorus recovery from black water

Source-separated black water (BW) (toilet water) containing 38% of the organic material and 68% of the phosphorus in the total household waste (water) stream including kitchen waste, is a potential source for energy and phosphorus recovery. The energy recovered, in the form of electricity and heat, is more than sufficient for anaerobic treatment, nitrogen removal and phosphorus recovery. The phosphorus balance of an upflow anaerobic sludge blanket reactor treating concentrated BW showed a phosphorus conservation of 61% in the anaerobic effluent. Precipitation of phosphate as struvite from this stream resulted in a recovery of 0.22 kgP/p/y, representing 10% of the artificial phosphorus fertiliser production in the world. The remaining part of the phosphorus ended up in the anaerobic sludge, mainly due to precipitation (39%). Low dilution and a high pH favour the accumulation of phosphorus in the anaerobic sludge and this sludge could be used as a phosphorus-enriched organic fertiliser, provided that it is safe regarding heavy metals, pathogens and micro-pollutants.     

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.     

Ammonium nitrogen removal from slurry-type swine wastewater by pretreatment using struvite crystallization for nitrogen control of anaerobic digestion.

Precipitation of ammonium together with phosphate and magnesium is a possible alternative for lowering the nitrogen content of wastewater. In this study we examine the removal of ammonium nitrogen and phosphorus from slurry-type swine wastewater containing high concentrations of nutrients by the addition of phosphoric acid along with either calcium oxide or magnesium oxide, which leads to the crystallization of insoluble salts such as hydroxyapatite and struvite. The struvite crystallization method showed a high capacity for the removal of nitrogen when magnesium oxide and phosphoric acid were used as the magnesium and phosphate sources, respectively. When it was applied to swine wastewater containing a high concentration of nitrogen, the injection molar ratio of Mg2+:NH4+:PO4(3-) that gave maximum ammonium nitrogen removal was 3.0:1.0:1.5.     

Removal of ammonium from aqueous solutions using the residue obtained from struvite pyrogenation

This paper reports the results of laboratory studies on the removal of ammonium from aqueous solutions using struvite pyrogenation residues. A series of experiments were conducted to examine the effects of the pyrogenation temperature (90-210 °C) and time (0.5-4 h) on the ammonium release of struvite. In addition, the pyrolysate of struvite produced at different pyrogenation temperatures and times was recycled for ammonium removal from aqueous solutions. The experimental results indicated that the ammonium release ratio of struvite increased with an increase in the pyrogenation temperature and time, and the struvite pyrolysate used as magnesium and phosphate source for ammonium removal was produced at the optimal condition of pyrogenation temperature of 150 °C for 1 h. Furthermore, experimental results showed that the optimum pH and pyrolysate dosage for ammonium removal from 100 ml synthetic wastewater (1,350 mg ammonium/L) were at pH 9 and 2.4 g of struvite pyrolysate, respectively, and initial ammonium concentration played a significant role in the ammonium removal by the struvite pyrolysate. In order to further reduce the cost of struvite precipitation, the struvite pyrolysate was repeatedly used for four cycles. The results of economic analysis showed that recycling struvite for three process cycles should be reasonable for ammonium removal, with ammonium removal efficiencies of over 50% and a reduction of 40% in the removal cost per kg NH(4)(+).     

Solutions to a combined problem of excessive hydrogen sulfide in biogas and struvite scaling.

The Woodman Point Wastewater Treatment Plant (WWTP) in Western Australia has experienced two separate problems causing avoidable maintenance costs: the build-up of massive struvite (MgNH4PO4. 6H2O) scaling downstream of the anaerobic digester and the formation of hydrogen sulfide (H2S) levels in the digester gas to levels that compromised gas engine operation and caused high operating costs on the gas scrubber. As both problems hang together with a chemical imbalance in the anaerobic digester, we decided to investigate whether both problems could be (feasibly and economically) addressed by a common solution (such as dosing of iron solutions to precipitate both sulfide and phosphate), or by using separate approaches. Laboratory results showed that, the hydrogen sulfide emission in digesters could be effectively and economically controlled by the addition of iron dosing. Slightly higher than the theoretical value of 1.5 mol of FeCl3 was required to precipitate 1 mol of dissolved sulfide inside the digester. Due to the high concentration of PO4(3-) in the digested sludge liquor, significantly higher iron is required for struvite precipitation. Iron dosing did not appear an economic solution for struvite control via iron phosphate formation. By taking advantage of the natural tendency of struvite formation in the digester liquid, it is possible to reduce the risk of struvite precipitation in and around the sludge-dewatering centrifuge by increasing the pH to precipitate struvite out before passing through the centrifuge. However, as the Mg2+/PO4(3-) molar ratio in digested sludge was low, by increasing the pH alone (using NaOH) the precipitation of PO4(3-) was limited by the amount of cations (Ca2+ and Mg2+) available in the sludge. Although this would reduce struvite precipitation in the centrifuge, it could not significantly reduce PO4(3-) recycling back to the plant. For long-term operation, maximum PO4(3-) reduction should be the ultimate aim to minimise PO4(3-) accumulation in the plant. Magnesium hydroxide liquid (MHL) was found to be the most cost-effective chemical to achieve this goal. It enhanced struvite precipitation from both, digested sludge and centrate to the point where more than 95% PO4(3-) reduction in the digested sludge was achieved.     

Applications and limitations of ADM 1 in municipal wastewater solids treatment.

The ADM 1 model has been implemented in a steady-state whole wastewater plant simulator. The ADM 1 model has been in use with good success for approximately 2 years on a wide range of wastewater treatment facilities. However, a number of modifications were necessary to allow it to be used in the context of municipal wastewater treatment. It was found that the model's use was greatly simplified if used in conjunction with a larger plant simulator to assist in the feed fractionation. It was also found that a better fit to actual operating data was achieved if some of the slowly biodegradable particulate fraction was partitioned into ADM particulate fractions other than the composite fraction. Another significant limitation of the model is in the absence of phosphorus modeling. The ADM model needs to have phosphorus handling for all the relevant fractions, and needs to include the handling of inorganic reactions such as struvite precipitation and metal phosphate/metal hydroxide precipitation. Activity effects on chemical equilibria are significant when considering phosphorus. Also of importance in wastewater treatment is the fate of sulfur compounds. This includes the generation of H2S in the digester gas and the fate of the sulfur species in the digested sludge (as a predictor of odour-generating potential).     

Phosphates in Lake Chapala, Mexico

Lake Chapala, the most important lake in Mexico, has suffered from cultural eutrophication problems for many years, manifested by the growth of aquatic vegetation and an increase in primary productivity. It was found that about 70% of the total phosphorus entering Lake Chapala is orthophosphate, thus increasing the biological availability of nutrients in the lake. In addition, the hydrologic imbalance in the lake, caused by the over‐use of water resources along the Lerma–Chapala basin, has significantly increased the hydraulic residence time of the inflow waters, thus increasing the effects of the added phosphorus, and creating conditions that increase the lake’s eutrophication status. The shallow characteristics of the lake and the action of the wind forces produce rapid changes in water quality, especially in the distribution of phosphate. The focus of this paper is on the development of a historical orthophosphate balance in Lake Chapala, quantifying the main point and non‐point sources that contribute to the enhancement of this nutrient in the lake. The estimation of the amount of phosphate in the lake can be used to determine appropriate management practices to reduce the phosphate loads on the lake.     

Evaluation and thermodynamic calculation of ureolytic magnesium ammonium phosphate precipitation from UASB effluent at pilot scale

The removal of phosphate as magnesium ammonium phosphate (MAP, struvite) has gained a lot of attention. A novel approach using ureolytic MAP crystallization (pH increase by means of bacterial ureases) has been tested on the anaerobic effluent of a potato processing company in a pilot plant and compared with NuReSys(?) technology (pH increase by means of NaOH). The pilot plant showed a high phosphate removal efficiency of 83 ± 7%, resulting in a final effluent concentration of 13 ± 7 mg · L(-1) PO(4)-P. Calculating the evolution of the saturation index (SI) as a function of the remaining concentrations of Mg(2+), PO(4)-P and NH(4)(+) during precipitation in a batch reactor, resulted in a good estimation of the effluent PO(4)-P concentration of the pilot plant, operating under continuous mode. X-ray diffraction (XRD) analyses confirmed the presence of struvite in the small single crystals observed during experiments. The operational cost for the ureolytic MAP crystallization treating high phosphate concentrations (e.g. 100 mg · L(-1) PO(4)-P) was calculated as 3.9 € kg(-1) P(removed). This work shows that the ureolytic MAP crystallization, in combination with an autotrophic nitrogen removal process, is competitive with the NuReSys(?) technology in terms of operational cost and removal efficiency but further research is necessary to obtain larger crystals.     

Model-based optimisation of the biological performance of a sidestream MBR.

A model-based optimisation of the operation in view of the biological performance in terms of nitrogen (N) and phosphorus (P) removal of a pilot-scale side-stream MBR has been performed by means of a two-tier scenario analysis. The methodology uses two different scenario analyses to simulate the effect of three degrees of freedom in the MBR system: (1) DO set-point in the aerobic reactor, (2) sludge residence time and (3) internal recirculation rate. The scenarios are simulated using a calibrated ASM2d MBR model. Effluent quality, in terms of nitrate, ammonia and phosphate, is used to select the best scenario. It proved to be a compromise between nitrogen and phosphorus removal as these are linked. A 42% reduction in ammonium and a 32% reduction in nitrate concentration were achieved. Phosphate removal is partly sacrificed (39% increase) compared to the standard operation.     

Chemical phosphorus removal to extremely low levels: experience of two plants in the Washington, DC area.

Chemical phosphorus removal using metal (iron and aluminium) salts is frequently used to control effluent soluble phosphorus levels in wastewater treatment plants. In the Washington DC area effluent phosphorus requirements are extremely stringent to protect the Chesapeake Bay. Full-scale data from two plants in the area were analysed to establish phosphate behaviour in the presence of iron. Titration experiments and mathematical modelling were performed to determine the role of ferric phosphate and hydroxide precipitation and other mechanisms that may potentially be involved in phosphorus removal. Iron addition is described in the model using a chemical equilibrium approach extended with surface charges and adsorption. The model verifies key observations from full-scale data: (a) extremely low orthophosphate levels can be achieved over a wide range of pH values, (b) a mixture of ferric phosphate and ferric hydroxide precipitate is forming with the hydroxide acting as sorbent, (c) molar ratios of Fe/P (iron dosed to phosphate removed) vary widely (1.0-3.9) based on the technology used and residual phosphate levels. The model will be a useful tool for engineers to optimise preliminary, simultaneous and tertiary P removal, both for design and plant operation.     

Occurrence of micro-organic pollutants on phosphorus recovery from urine

Increased population growth and food prices have resulted in more demand for fertilizers, especially phosphorus (P), to be used in agriculture and production of food crops. Phosphorus is one of the important natural resources and will be exhausted in the near future. Nowadays, struvite production is a good method to recover P from urine. However, the natural urines contain high amounts of micro-organic pollutants which may cause health risks. Therefore, in this contribution, we investigated the amount of micro-organic pollutants in struvite from urine. There are various kinds of pharmaceuticals and hormones which are used in the world. Nevertheless, we focused on 10 pharmaceuticals (amoxycillin, carbamazepine, erythromycin, furosemide, atenolol, ibuprofen, norfloxacin, trimethoprim, tetracycline, and acetylsalicylic acid) and one hormone (17β-estradiol) as representatives. The experiments were carried out with synthetic and natural urines. After the production of struvite, the results from synthetic and natural urine samples showed that only tetracycline, erythromycin, and norfloxacin remained in the struvite, and, especially, tetracycline remained in struvite with quite a high amount.     

Effects of various process parameters on struvite precipitation kinetics and subsequent determination of rate constants.

In this paper, struvite (MgNH(4)PO(4).6H(2)O) precipitation kinetics were studied with different operating conditions (varying supersaturation, pH, Mg:P ratio, degree of mixing and seeding conditions) and relevant rate constants were determined by fitting a slightly modified first-order kinetic model to the experimental data obtained. The rate of change of ortho-P concentration in the bulk solutions increases with increasing supersaturation ratio. The estimated rate constants are 2.034, 1.716 and 0.690 hr(-1) for the supersaturation ratio of 9.64, 4.83, and 2.44, respectively. Kinetic parameters were also evaluated for the Mg:P ratio between the ranges of 1.0 and 1.6, indicating higher phosphorus removal efficiency with increasing Mg:P ratio. The rate constants were found to be 0.942, 2.034 and 2.712 hr(-1) for Mg:P ratios of 1.0, 1.3 and 1.6, respectively. The experimental observations for kinetic study of struvite precipitation with different stirrer speeds clearly show that the mixing intensity used had little effect on the intrinsic rate constants. K values found to be 2.034 and 1.902 h(-1) for 100 and 70 rpm, respectively. Seeding, with 250-500 microm of seed crystals during the struvite precipitation kinetics test, was found to have very little effect on the ortho-P removal.