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Fertilizer-Grade Calcium Phosphate Recovery from Wastewater

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Fertilizer-Grade Calcium Phosphate Recovery from Wastewater Fertilizerili ‐GdGrade CliCalcium Phosphatehh Recovery Amanda Boyce, MSc Phillip Barak, PhD AmandaAmanda.Boyce Boyce@ [email protected] WisconsinWisconsin.gov gov FFrom WWastewater TTreatment PlPlants ABSTRACT MATERIALS & METHODS RESULTS CONT’DCONT D Phosphorus removal and recovery from wastewater treatment have focused on producing The chemical modeling program ‘MinteqMinteq for Windows v1v1.5 5’ was utilized to calculate the mineral In accordance with chemical modelingmodeling, phosphorus struvite from the gravitygy belt thickened filtrate throughg the addition of Mg(OH)g( )2. This studyy solubility,y, and thus the mineral formation potential,p, for various portionsp of the multiphasep precipitationpp from syntheticy OA solution in the endeavored to improve on this recovery system by producing calcium phosphates from anaerobic digestion process at the Madison Metropolitan Sewage District wastewater treatment flfluidized idi d bdbed reactort idincreased withith pHH tto 656.5 andd organic acid (OA) digest through the addition of Ca(OH)2 using a fluidized bed reactor (FBR). plant. Based on this analysis, synthetic organic acid solution was allowed to react in a fluidized bed ~9090% P recovery was achieved (Fig(Fig. 4)4). ThiThis studyd diddetermined thath producingdi calciumli phosphateshh was an efficientffi i recovery system, reactor withih calciumli hdhydroxide id slurryl at variousi pHH valuesl iin orderd to produced calciumli X‐ray diffraction of the solid product showed that with 90% P recoveryrecovery, and could be achieved in less alkaline conditions than those required for phosphatesphosphates. In a benchtop‐scale fluidized bed reactor (Fig(Fig. 2) with a hydraulic residence time of 33 brushite was the dominant mineral formed (Fig.(g 5).) struvite. Throughg X‐rayy diffraction and computerp modeling,g, it was determined that brushite,, a min,, various rates of Ca(OH)()were added to the flow of syntheticy OA digestg solution. 2 StSeparate bthbatch studiestdi withith reall OA didigest t confirmfi calciumli phosphatehht mineral,il was produced.dd 50 µm 90% reduction of soluble P as brushitebrushite. Figure 2. Benchtop Height 29.54cm Fluidized Bed Reactor ID 20.32cm used to test synthetic Height 7.62cm 100 solution (schematic( and INTRODUCTION photo)p) Height 42.55cm 90 TlTotal ID 10.16cm %) Height 178.44cm id (% At present rates of consumptionconsumption, the world may face P shortages within the next 90 years HihtHeight 5.72cm Gear pump Sol HihHeight 40.64cm Flow Control 80 ID 5.72cm Device (Vaccari, 2009). Recovery of P from wastewater treatment plants is one way to extend the y as MiMixing i UUnit it withith Flow Control Centrifuge very supplyl off virginii P mineralil resources. PiPrevious studiesdi ((e.g., LLe‐CCorre, 2009) hhave primarilyiil pH probe Device Pump 70 ecov Height 25.4cm focused on recovering P as struvitestruvite, NH4MgPO4∙6H2OO, from the gravity belt thickener (GBT) ID 5.72cm Total Collection Height 51.13cm P ReP DiffDifferential ti l Analysis A l i Collection 60 Solid Product filtrate,, located at the end of the anaerobic digestiong processp byy maintainingg pHp between 8.5‐ Vessel 888.8 and adding an additional source of magnesium (Mg)(Mg). 505.0 555.5 606.0 656.5 707.0 757.5 808.0 pH Figure 5. Micrograph (top) of solid product RESULTS Figure 4. 4 Measured P recovery as a percentage of at pH 7.0 and x-ray diffraction pattern In recent years, multiphase anaerobic digestion influent PP, based on difference between influent and compared with brushitebrushite, CaHPO4·2H2O At the Madison Metropolitan Sewage District, the OA digest had a significantly greater soluble P systems (Fi(Fig. 1) hhave bbeen iddintroduced to effluent P concentrations and solid product recovered. recovered (bottom)(bottom). concentration,i 1818.57 57 mMM (572 ppm),) thanh theh GBT filfiltrate, 5185.18 mMM (161 ppm),) andd thereforehf theh wastewater treatment facilitiesfacilities, with the goal of P recovery potential was greatest for the OA digestdigest. Minteq for Windows predicted that the CONCLUSIONS optimizingpg acetogenesisg in an organicg acid (OA)() soluble,, reactive P in the OA digestg could be recovered as either brushite,, a calcium phosphatepp ThThe purpose off thithis studytd was tto dtdetermine i ththe potentialttil ffor calciumli phosphatehht recovery ffrom digester to be followed by optimized mineral,il ththrough h ththe additiondditi off C(OH)Ca(OH) tto pHH 666.6 (Fi(Fig. 3A)3A), or as struvite,tit a magnesiumi the OA digest and quantify how changes in pH would effect such a systemsystem. This study concluded methanogenesis in a thermophilic digesterdigester, with 2 phosphate mineralmineral, through the addition of Mg(OH) to pH 858.5 (FigFig. 3B)3B). that: an ultimatel purpose off greater methaneh generation 2 1. Theh OA ddigest hdhad threeh times more solublelbl, reactive P concentration thanh GBT flfiltrate. and higher quality biosolids with a lower pathogen 2. ChChemical i l modelingdli predicteddi t d thithis solublelbl P couldld bbe recoveredd as bhitbrushite bby addingddi C(OH)Ca(OH) . 1 loadoad foro moreoe widespreaddesp ead distribution.d st but o 1 20 20 2 Figure 11. Typical multistage digestion - - Brushite M(OH)Mg(OH) Ca(OH) L L Calcite 2 2 wastewater treatment facilityfacility, based on the BhiBrushite Struvite 3. Brushite formation successfully removed 90% of P in synthetic OA digest solution and could Calcite Madison Metropolitan Sewage District (MMSD) mol mol 15 15 mm Struvite operation mm be achieved at a much lower pHpH, ideally at 656.5, than struvite formationformation, pH 858.5‐888.8. d, m d, m med 4. Removal and recovery of P in the OA digester would decrease the incidence of nuisance med 10 10 orm form ftiformation off struvitetit iin ththe tttreatment t plantlt andd reduced P ldload iin bibiosolids. lid s fo es f ate OBJECTIVES ate 5 5 pita 11. DiDetermine theh theoreticalhil P recovery potentialil off theh OA didigest. pita ACKNOWLEDGEMENTS eci ecip Pre The authors gratefully acknowledge the support of USDA‐NIFA Hatch WIS01352, the University of Wisconsin‐Madison 22. Determine how solution pH impacts the recovery and speciation of P minerals produced PreP 0 0 0 20 40 60 80 100 120 140 0 20 40 60 80 100 120 140 Graduate School, and Madison Metropolitan Sewage District. at the benchtopp scale. Base Added, mmol (OH)() L-11 Base Added, mmol (OH) L-11 REFERENCESS Le‐Corre, K., E. Valsami‐Jones, P. Hobbs, and S. Parsons. 2009. Phosphorus Recovery from Wastewater by Struvite Crystallization. Environmental Technology FiFigure 3A3A. PPredicted di t d mineral i l precipitation i it ti with ith FiFigure 3B3B. PPredicted di t d mineral i l precipitation i it ti with ith 39:433‐477. C(OH)Ca(OH)2 additiondditi tto OA didigest. t M(OH)Mg(OH)2 additiondditi tto OA didigest. t Vaccari, D. A. 2009. Phosphorus: A Looming Crisis. Scientific American. 300:54‐59..
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