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Lectures Vaccari - Physicochemical Nutrient Recovery Technologies

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Lectures Vaccari - Physicochemical Nutrient Recovery Technologies

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Lectures Vaccari - Physicochemical Nutrient Recovery Technologies

  1. 1. Physicochemical Nutrient Recovery Technologies David A. Vaccari dvaccari@stevens.edu Cities of the Future Lago di Como May 13, 2016
  2. 2. Outline • Nitrogen removal and recovery – Stripping and Scrubbing • Phosphorus precipitation – Direct precipitation – Crystallization • Incinerator ash – Leaching/extraction – Thermal 2
  3. 3. Buckwell, A. Nadeu, E. 2016. Nutrient Recovery and Reuse (NRR) in European agriculture. A review of the issues, opportunities, and actions. RISE Foundation, Brussels.
  4. 4. Ammonia Stripping/Scrubbing 4 NH4 +  NH3 pKa = 9.24 NH4 + NH3
  5. 5. Ammonia Stripping/Scrubbing (Nitrification must be avoided) 5 NH4 + NH3 Caustic Air H2SO4 NH4SO4 or HNO3 or NH4NO3
  6. 6. Anaerobic/Ion Exchange (AN-IX) Anaerobic Solids Blanket ammonification to NH4 + Ion Exchange Chambers zeolite granular ion exchange media Sanitation Water Low Nitrogen Effluent CH4, H2 Daniel P. Smith, Ph.D., P.E., DEE Applied Environmental Technology, Garrett Park, Maryland
  7. 7. Phosphorus Removal and Recovery 7 • Mainstream processes • 40% to 50% recovery • Sludges, manure, etc. • 90% recovery possible • 50-60 mg P/L required • 75-300 mg P/L typical in BNR • Incinerator ash • 90% recovery typical E. Desmidt et al, Phosphorus Scarcity and P-Recovery Techniques (U. Gent, 2014)
  8. 8. Phosphorus precipitation 8 10 Ca2+ + 6 PO4 3- + 2 OH- ↔ Ca10(PO4)*6(OH)2 ↓ http://www.lenntech.com/phosphorous-removal.htm Al3+ + HnPO4 3-n ↔ AlPO4 + nH+ Fe3+ + HnPO4 3-n ↔ FePO4 + nH+ Iron and Aluminum phosphorus precipitates are not readily bioavailable and therefore not favored for fertilizer use
  9. 9. Forms of Calcium Phosphate 9 E. Desmidt et al, Phosphorus Scarcity and P-Recovery Techniques (U. Gent, 2014) Phase formed is kinetically determined DCPD forms preferentially at pH 5 OCP around pH 6 HAP above pH 7 HAP is most stable phase and ultimate form
  10. 10. http://www.lenntech.com/phosphorous-removal.htm Post-precipitation can give P < 0.5 mg/L Co-precipitation has low capital costs, but P ~ 1 mg/L Pre-precipitation
  11. 11. Buckwell, A. Nadeu, E. 2016. Nutrient Recovery and Reuse (NRR) in European agriculture. A review of the issues, opportunities, and actions. RISE Foundation, Brussels.
  12. 12. Substance Conc. (mg/L) Conc. (mmolar) PO4-P 87 2.8 Ca+2 51 1.3 Mg+2 7.2 0.3 NH4+N 1142 81.6 CO3 (as CaCO3) 1068 10.7 Chemical Composition of Anaerobic Digester Effluent (Jie Ge and Xiaoguang Meng) Struvite Mg++ 18% NH4+ - N 10% PO4-3 - P 23% Dolomite Calcined Ca 22% 42% Mg 13% 25%
  13. 13. DL is provided by Graymount Lime Inc. Ca and Mg content in DL were 39.9% and 22.4%, respectively. 13 Dolomite Lime (CaMg(OH)4) Dolomite Dolomite Lime Calcined DL Components phase Molecular formula Wt. % Periclase MgO 28.3 Portlandite Ca(OH)2 58.4 Brucite Mg(OH)2 12.3 Calcite CaCO3 1.0
  14. 14. Kinetic experiments 14 P N Mg Ca Mg2+ + NH4 + + PO4 3 + 6H2O  MgNH4PO46H2O Ca2+ + PO4 3- + OH-  Ca5(PO4)3OH P in the effluent water = 98 ppm
  15. 15. Removal of Phosphate Using a Dolomite Lime (CaMg(OH)4) in a Complete Mix Reactor 9 0 20 40 60 80 100 0 8 16 24 32 40 48 PO4 3--P(mg/L) Time(h) A 0.1g/L DL 0.3g/L DL 0.5g/L DL 0.8g/L DL 0.3 g/L lime 7 7.5 8 8.5 9 0 8 16 24 32 40 48 pH Time (h) B 0.1 g/L DL 0.3 g/L DL 0.5 g/L DL 0.8 g/L DL 0.3 g/L lime 0 20 40 60 80 100 0 8 16 24 32 40 48 Ca2+(mg/L) Time (h) C 0.1 g/L DL 0.3 g/L DL 0.5 g/L DL 0.8 g/L DL 0.3 g/L lime 0 50 100 150 200 0 8 16 24 32 40 48 Mg2+(mg/L) Time (h) D 0.1 g/L DL 0.3 g/L DL 0.5 g/L DL 0.8 g/L DL 0.3 g/L lime
  16. 16. SEM Images and XRD Spectra of the Solid Products 1 6 Chemical analysis of the solids: 23% P, 11% N, 4% K. The product contains high contents of the nutrients. S=struvite C=calcite
  17. 17. Current Treatment Technologies for Point Source Discharge (Courtesy Chelskey Shepsko & Arun SenGupta • Electrodialysis / Reverse Osmosis Source: FuMA-Tech, 2016.
  18. 18. WAC and HAIX-Zr Ion Exchange Process for Removal
  19. 19. HAIX-NanoZr Synthesis
  20. 20. HAIX-NanoZr Design Cation exchanger with negatively charged sulfonic acid groups as the host resin. Anion exchanger with positively charged quaternary ammonium groups as the host resin. The synergy of highly durable polymer support, Donnan Membrane Principle, and zirconium oxide nanoparticles
  21. 21. Phosphorus Regeneration for HAIX Column with WAC Phosphate free water Phosphate loaded water•Process to create struvite o Regenerate with NH4OH o Added stoichiometric MgCl2 to regenerant
  22. 22. Some Commercially Available Full-Scale Processes 22 E. Desmidt et al, Phosphorus Scarcity and P-Recovery Techniques (U. Gent, 2014)
  23. 23. 23 Mg2+ + NH4 + + PO4 3- MgNH4PO4∙6H2O Accidental Struvite Formation (courtesy of Michael Ditton, Ostara Co.)
  24. 24. 24 Fluidized Bed Struvite Precipitation
  25. 25. 25 Phosphorus Recovery Intercepts Recycle to Recover Phosphorus and Ammonia (courtesy of Michael Ditton, Ostara Co.)
  26. 26. 26 WASSTRIP Increases P Recovery while protecting Digesters from Struvite Formation (courtesy of Michael Ditton, Ostara Co.)
  27. 27. 27 Crystalized Struvite Product (courtesy of Michael Ditton, Ostara Co.)
  28. 28. Ostara Pearl® STRUVITE PRECIPITATION ALTERNATIVES Multiform Harvest Kansas Environmental Management Associates (KEMA) Phred™
  29. 29. Crystallactor 29
  30. 30. Incinerator Ash Vlasta Klima Balloun Lecture
  31. 31. Seaborne Process Recovery of P and N; Removal of Heavy Metals Energy Recovery by Incineration of Biosolids 31
  32. 32. Outotec – Ash Dec Process 32 http://www.chemengonline.com/p-recovery-on-the-move/?printmode=1 • 1000 degrees C • Toxic metals are vaporized – reducing 99% less Cd and 90% less U content of product than fertilizer from phosphate rock (suitable for organic farming) • Product is calcined phosphate – combined with K salts to make fertilizer
  33. 33. Mephrec Process 33 • Coke and oxygen inputs (reducing conditions) • 1450 degrees C • Heavy metals are reduced to metallic state • Utilizes energy content of sludge • Produces calcium-silico- phosphate fertilizer http://www.chemengonline.com/p-recovery-on-the-move/?printmode=1
  34. 34. Conclusion: Nutrient Removal and Recovery is Hot! May 16, 2016 AAEES Nutrient Recovery Workshop New Jersey Water Environment Association Annual Conference, Atlantic City, NJ July 10-13, 2016 WEF/IWA Nutrient Removal and Recovery The Hyatt Regency Denver - Convention Center Denver, Colorado 34
  35. 35. What do you think? David A. Vaccari dvaccari@stevens.edu

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