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.     

Fate of pharmaceuticals and bacteria in stored urine during precipitation and drying of struvite

Experiments were conducted to measure the behaviour of eight pharmaceuticals during urine treatment as part of the project 'SANIRESCH - Sustainable sanitary recycling Eschborn'. Urine was collected from 200 people in a public building via waterless urinals and NoMix toilets. It was then stored at room temperature at different pH values to analyse the extent to which bacteria and pharmaceuticals are eliminated over time. Although a partial elimination of pharmaceuticals could be detected, the storage at defined pH values cannot be advised. As the persons tested used pharmaceuticals with different structures, in different amounts and at varying intervals, this method of treatment is insufficient for removing them from urine. Precipitating the urine with MgO, washing it with saturated struvite solution and drying it at 30 °C will result in a free-flowing granular powder of struvite (NH(4)MgPO(4)·6H(2)O) that is free of pharmaceuticals and pathogens and can be used as fertiliser and a source of nitrogen, magnesium and phosphorus.     

Phosphorus recovery as struvite from eutropic waters by XDA-7 resin

Phosphorus releases into aquatic environment and its subsequent contribution to eutrophication have resulted in a widespread global pollution issue. However, phosphorus is a non-renewable source. The potential supplies of phosphorus are decreasing worldwide. Therefore, removal and recovery of phosphorus from the eutropic waters is important, emergent and necessary. In this research, experiments for recovering phosphate from eutropic waters by anion exchange combined with struvite precipitation were conducted. The results indicated that the prepared XDA-7 resin was an effective adsorbent for phosphate. The adsorption isotherm of XDA-7 resin was found to be a modified Freundlich type. The maximum phosphate adsorption (20.9 mg/g) occurred in the pH range of 6.0-8.0. Phosphate adsorbed on the XDA-7 resin was effectively desorbed with 8% NaCl solution, and the resin was able to be regenerated with 3% NaClO and 4% NaOH solutions. Phosphate desorbed from the resin was recovered as magnesium ammonium phosphate (struvite). The obtained struvite was analyzed by acid dissolution method, scanning electron microscope (SEM) and Fourier transform infrared spectroscopy (FTIR). The struvite precipitate was found to be 75.8% in purity, a high-value fertilizer.     

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.     

Phosphorus recovery from anaerobic digester supernatant by struvite crystallization: model-based evaluation of a fluidized bed reactor

This paper is an attempt to model the UBC (University of British Columbia) MAP (Magnesium Ammonium Phosphate) fluidized bed crystallizer. A mathematical model is developed based on the assumption of perfect size classification of struvitre crystals in the reactor and considering the movement of liquid phase as a plug flow pattern. The model predicts variation of species concentration of struvite along the crystal bed height. The species concentrations at two extreme ends (inlet and outlet) are then used to evaluate the reactor performance. The model predictions provide a reasonable good fit with the experimental results for both PO4-P and NH4-N removals. Another important aspect of this model is its capability of predicting the crystals size and the bed voidage at different height of the reactor. Those predictions also match fairly well with the experimental observations. Therefore, this model can be used as a tool for performance evaluation of the reactor and can also be extended to optimize the struvite crystallization process in the UBC MAP reactor.     

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.     

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.     

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.     

Removal of ammonium from human urine through ion exchange with clinoptilolite and its recovery for further reuse.

Ammonium, from separately collected human urine, had been removed through transfer onto the ammonium selective natural zeolite, clinoptilolite, through ion exchange. In the subsequent treatment steps of washing with tap water, ammonium removed from urine was eluted from the surface of the clinoptilolite to be recovered for further reuse. Different quantities of clinoptilolite were used for a survey of the capacity of the zeolite for the process and to identify removal efficiencies based on initial ammonium loads. The highest surface concentration attained under experimental conditions employed was 15.44 mg ammonium per gram of clinoptilolite for an initial concentration of 110 mg ammonia per litre, and the highest removal was 98%, obtained for a loading of 1 mg ammonium per gram clinoptilolite. In the subsequent elution process, better removals were observed as pH was increased and the highest removal was attained at pH 13. The recovery was calculated as 9.73 mg ammonium per gram of clinoptilolite, corresponding to an efficiency of 63% only through washing with tap water. The results have given positive indications for the possibility of using ion exchange with clinoptilolite for the removal of ammonium from human urine and an incentive for improving methods of elution for its recovery for further reuse.     

Phosphorus recovery by mesoporous structure material from wastewater.

This study was designed to investigate the fundamental aspects of a possible removal of phosphorous from wastewater by using the mesoporous structure materials for wastewater reuse. The zirconium sulphate with mesoporous structure as a new type of ion exchangers was synthesised by hydrothermal reaction. From the results of X-ray diffraction and transmission electron microscope, it was discovered that the synthesised material had hexagonal mesoporous structure with a pore size of approximately 40-50A. Experimental results showed that the zirconium sulphate with mesoporous structure had very high sorption capacity for the phosphorus. The novel ion exchange occurred between PO4(3-) and SO4(2-), OH-. The amount of phosphate ions exchanged into the solid was as great as 3.4 mmol/g-ZS. Furthermore, it is possible to obtain a higher removal efficiency than other ion exchange media and adsorbents.     

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.     

Nitrogen removal from the saline sludge liquor by electrochemical denitrification.

Sludge liquor from the sludge dewatering process has a high ammonia content. In the present study, a lab-scale electrochemical (EC) system with a pair of Ti electrode plates was used for treating the sludge centrate liquor of digested wastewater sludge with a NH4(+) - N content of around 500 mg/L. The sludge liquor had a high salinity due to seawater being used for toilet flushing in Hong Kong. The results show that the EC process is highly effective for denitrification of the saline sludge liquor. Complete nitrogen removal could be achieved within 1 hr or so. The rate of EC denitrification increased with the current intensity applied. The best current efficiency for nitrogen removal was obtained for a gap distance between the electrodes at 8 mm. Electro-chlorination was considered to be the major mechanism of EC denitrification. The formation of chlorination by-products (CBPs) appeared to be minimal with the total trihalomethanes (THM) detected at a level of 300 microg/L or lower. The power consumption for EC denitrification was around 23 kWh/kg N. Additional electro-flocculation with a pair of iron needle electrodes could enhance the flocculation and subsequent sedimentation of colloidal organics in the sludge liquor, increasing the organic removal from less than 30% to more than 70%. Therefore, the EC process including both electro-denitrification and electro-flocculation can be developed as the most cost-effective method for treatment of the saline sludge liquor.     

Nitrogen and phosphorus removal from swine wastewater by intermittently aerated dynamic-flow system.

This study was performed to evaluate the effects of the volume fraction of an anaerobic reactor (VFAR) and SRT on the removal of T-N and T-P in both an intermittently aerated system (IAS) and intermittently aerated dynamic-flow system (IADS), respectively. When the VFAR in the total volume of reactor from both IAS and IADS are 13%, 7%, and 0% at 5 days of SRT, the removal efficiencies of T-P were 80-87%, 62-65% and <30%, respectively. However, it was observed from this study that the removal efficiencies of T-N and T-P were not correlated to VFAR at a predetermined SRT, producing greater than 5000 mg/L of MLVSS. Also, IADS was shown to have the greater buffer capacity and adaptability to resist the shock due to the loading of high concentration of N. Furthermore, IADS achieved over 80% of removal efficiency of N even at much lower C/N ratio of 4.7. Therefore, it seems that IADS has the significant advantages over other biological nutrients removal processes.     

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.     

Ammonia recovery from anaerobically digested cattle manure by steam stripping.

Ammonia recovery from anaerobically digested cattle manure effluents through steam stripping was studied at a stripping tower temperature of 98-99 degrees C and a steam-water ratio approximately 56-72 g/L. The digested manure effluents were first treated by microfiltration and then the permeate was used as feed in steam stripping. The stripping performance was evaluated under different feed pH values, ammonia concentrations and temperatures. The increase of the initial feed pH does not significantly improve ammonia stripping efficiency due to the fact that the stripped effluent pH is increased during steam stripping. This suggests that steam stripping of anaerobically digested manure effluents for ammonia recovery may not need pre-raised pH. In contrast, the pH value of the synthetic ammonia wastewater containing NH4Cl dramatically decreases after steam stripping. Increasing the feed temperature slightly improves ammonia stripping efficiency, but reduces the concentration of the recovered ammonia in the condensate due to an increased condensate volume at a higher feed temperature. Therefore, the feed temperature should be controlled at an optimum point that can compromise the condensate ammonia concentration and the ammonia stripping efficiency. Experimental results indicate that recovery of ammonia from anaerobically digested cattle manure effluents as NH4OH is technically feasible.     

Direct energy recovery from primary and secondary sludges by supercritical water oxidation.

Supercritical water oxidation (SCWO) oxidizes organic and biological materials virtually completely to benign products without the need for stack gas scrubbing. Heavy metals are recovered as stabilized solid, along with the sand and clay that is present in the feed. The technology has been under development for twenty years. The major obstacle to commercialization has been developing reactors that are not clogged by inorganic solid deposits. That problem has been solved by using tubular reactors with fluid velocities that are high enough to keep solids in suspension. Recently, system designs have been created that reduce the cost of processing sewage sludges below that of incineration. At 10 wt- % dry solids, sludge can be oxidized with virtually complete recovery of the sludge heating value as hot water or high-pressure steam. Liquid carbon dioxide of high purity can be recovered from the gaseous effluent and excess oxygen can be recovered for recycle. The net effect is to reduce the stack to a harmless vent with minimal flow rate of a clean gas. Complete simulations have been developed using physical property models that accurately simulate the thermodynamic properties of sub- and supercritical water in mixtures with O2, N2, CO2, and organics. Capital and operating cost estimates are given for sewage sludge treatment, which are less costly than incineration. The scenario of direct recovery of energy from sludges has inherent benefits compared to other gasification or liquefaction options.     

Phosphorus removal and recovery from wastewater by tobermorite-seeded crystallisation of calcium phosphate.

Investigations were focused on the development of a technology for phosphorus (P) recovery straight from wastewater. Facing the finiteness of the natural resources of this essential nutrient, the declared goal must be the sustainable use of available phosphorus sinks such as wastewater treatment plants (WWTP) for the generation of P rock substitutes. A feasible method for simultaneous elimination and recovery of phosphorus from wastewater proved to be the P-RoC process - the phosphorus recovery from wastewater by induced crystallisation of calcium phosphate, applying tobermorite-rich waste compounds of the construction industry. The experiments were performed in fixed bed-, stirred- and expanded bed reactors in laboratory--as well as in pilot-scale experiments. The efficiency and longevity of the P-RoC process was determined by the supply of Ca ions and the initial P concentration. Total P (P-tot) contents in the generated crystallisation products of up to 13% P-tot (30% P2O5) were achieved. Mineralogical investigations proved the formation of a hydroxy-apatite-(HAP)-like coating onto the seed material's surface. Reuse options for the generated crystallisation products, such as substitute for phosphate rock or as new fertiliser, were assessed.     

以磷酸钙盐形式从内循环反应器中回收磷的初步研究

为探讨连续流内循环反应器以磷酸钙盐形式从污泥厌氧消化液中回收磷的工艺条件,考察了pH、Ca/P摩尔比、曝气强度和水力停留时间等因素对磷回收工艺过程的影响.结果表明,在污泥厌氧消化液总磷浓度86～108 mg/L、正磷浓度66～80 mg/L的条件下,保持反应体系pH9.0～9.5、Ca/P摩尔比2.0、水力停留时间45 min、曝气强度0.014 L/(L·min),内循环反应器磷的回收率接近90%,同时回收产品中磷的含量(以P2O5计)达到22.15%,可以作为磷肥生产原料.     

Concentration of nutrients from urine and reject water from anaerobically digested sludge.

Experiments with concentration of nutrients from source separated urine and reject water from digestion of sludge in sewage treatment plants (STP) have been performed in laboratory and pilot scale. The methods tested were membrane filtration with reverse osmosis (RO), evaporation, and precipitation of phosphorus and distillation of ammonia. In membrane filtration, pre-filtration with particle separation at 5-10 microm was enough to avoid clogging of the membranes. Separation of phosphorus (P), potassium (K) and sulphur (S) was almost 100%, while separation of nitrogen (N) was dependent on pH. The capacity of flux increased with temperature and pressure. In evaporation, all P, K and S were still in the concentrate, while pH had to be decreased to 4.5 to avoid significant loss of N. In precipitation and distillation, about 90% of P could be recovered from urine as magnesium ammonium phosphate (MAP) just by adding MgO. For the reject water pH was first increased by aeration to remove CO2. Ammonium can be distilled from the water phase after precipitation of MAP, without further increase of pH. At least 80-90% of N can be distilled in 5-10% of the total volume. The article also discusses the quality of different products, cost of separation, and energy and chemical demand.     

Energy and nutrient recovery from sewage sludge via pyrolysis.

Energy recovery and nutrient reuse from sewage sludge has traditionally been achieved via anaerobic digestion/power generation with land application of the biosolids. By contrast, thermal processes such as pyrolysis have typically been used only for energy recovery. One such technology has demonstrated at commercial scale that all of the energy in sludge can be beneficially recovered and reused. No attempt was however made to recover and reuse sludge nutrients. There are many potential benefits of using pyrolysis for both energy and nutrient recovery. Firstly, unlike digestion, the principal energy product is oil, which can readily be stored and used when required, ensuring that energy recovery is maximised. Secondly is that the sludge nutrients are recovered in the pyrolysis char. Laboratory soil incubation studies using char from the Subiaco demonstration plant were conducted over an eight-week period to confirm nutrient availability. Results from this study showed that the phosphorus in the char is plant available although the nitrogen was insoluble. Based on these results it appears that there is potential to use pyrolysis as an effective means to recover and reuse both the energy and the very valuable phosphorus present in sewage sludges.