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Phosphorus recovery and VFAs production from sewage sludge fermentation Natalia Herrero Garca D. Crutchik, N. Frison, A. Jelic and F. Fatone Background Background Municipal wastewater contains around 100 120gCOD/(inhabitant per day);


  1. Phosphorus recovery and VFAs production from sewage sludge fermentation Natalia Herrero García D. Crutchik, N. Frison, A. Jelic and F. Fatone

  2. Background Background Municipal wastewater contains around 100 ‐ 120gCOD/(inhabitant per day); • • Up to now, the utilization of sewage sludge has been limited mainly to the production of biogas for co ‐ production of thermal and electric energy and compostable material ; • The sewage sludge might be considered as a challenging feedstock to be processed for bio ‐ based applications (waste ‐ to ‐ chemicals and bio ‐ product value chain); • Volatile Fatty Acids (VFAs) could be considered intermediates for a wide range of applications

  3. Production & Application of Waste ‐ derived VFAs Production & Application of Waste ‐ derived VFAs Organic ‐ rich Wastes Pretreatment of Waste Anaerobic technologies for VFA production Operating conditions ‐ ph The operating conditions for VFAs production ‐ Temperature ‐ Hydraulic retention time should be addressed based on the final ‐ Solids retention time application of the VFAs ‐ Organic loading rate ‐ Additives Volatile fatty acids (VFA) Proper process control can manipulate the type Applications: ‐ Polyhydroxyalkanoates of VFA produced, which is critical to the ‐ Electricity performances of the downstream applications. ‐ Biogas ‐ Hydrogen ‐ Lipids for Biodiesel ‐ Biological nutrient removal Lee et al., 2014. Chemical Engineering Journal.

  4. Scenario: Integration of VFA Production and Scenario: Integration of VFA Production and Phosphorus Recovery Phosphorus Recovery Magnesium hydroxide T=37ºC Mg(OH) 2 PS Fermentation S/L SCFAs (SSFL) PS&WAS of Sewage Sludge WAS ‐ Acetic Acid; ‐ Propionic Acid; (After Dynamic ‐ Butyric Acid; Thickening) ‐ Others Struvite (MgNH 4 PO 4 ∙ 6H 2 O) To anaerobic digester

  5. Role of SCFAs in Wastewater Treatment Role of SCFAs in Wastewater Treatment • SCFAs are rbCOD and help the denitrification processes ; • Enhanced Bio ‐ P removal ( 4 ‐ 5 mgVFA are required for each mg P removed); • Hydrogen production ; • Biological Nutrients Removal ; • Lipids for biodiese l; • Polyhydroxyalkanoates (PHAs). Lee et al., 2014. Chemical Engineering Journal.

  6. Phosphorus Recovery Via Struvite Cristallyzation Phosphorus Recovery Via Struvite Cristallyzation Mg 2+ + NH 4 + + H n PO 4 n ‐ 3 + 6 H 2 0 MgNH 4 PO 4 ∙ 6H 2 0 + nH + Addition of Mg(OH) 2 as magnesium ion source and struvite seed crystals (5 g/L) to promote reaction. Initial pH fixed at pH 8.5 by addition NaOH Crutchik et al,. 2013  Struvite: High comercial value as slow release fertilizer

  7. Objective Objective • To study the effect of the sludge type and the initial fermentation pH on the production and composition of SCFAs; • To evaluate the feasibility of phosphorus recovery (as struvite, NH 4 MgPO 4 ∙ 6H 2 O) from sewage sludge fermentation liquid (SSFL); • To validate effect of initial pH and sludge type in propionate production and phosphorus recovery, best operating conditions were evaluated in a bench ‐ scale sequencing batch fermentation reactor

  8. Characteristics of the PS, WAS and PS&WAS Characteristics of the PS, WAS and PS&WAS Origin: WWTP of Verona municipality (North of Italy); Type of Dynamic Thickening: • Gravity Belt thickening for Primary Sludge; • Screw Drum for Waste Activated Sludge (6 ‐ 8 g polyacrilamide /kgTS) Parameter Units PS PS&WAS WAS g/L TS 29.7 ± 0.6 39.1 ± 0.8 58.1 ± 0.4 g/L VS 23.6 ± 0.5 33.5 ± 0.7 45.9 ± 0.5 mgCOD/gTVS Total COD 846.4 ± 4.0 914.8 ± 3.8 997.4 ± 6.1 mgN/gTVS Total Nitrogen (TN) 32.5 ± 0.8 41.9 ± 0.7 56.2 ± 0.5 mgN/gTVS Total Phosphorus (TP) 17.2 ± 0.4 17.5 ± 1.6 18.7 ± 1.1 gCOD/gN COD/N ratio 26.6 21.8 18.7

  9. Outline of the Batch Fermentation Experiments Outline of the Batch Fermentation Experiments N° Sludge COD/N Initial fermentation pH Experiment Type (gCOD/gN) 1 ‐ 5 PS 26.6 4.96 (Uncontrolled),8,9,10,11 6 ‐ 10 PS&WAS 21.8 5.76 (Uncontrolled),8,9,10,11 11 ‐ 15 WAS 18.7 6.19 (Uncontrolled),8,9,10,11 The response surface methodology (RSM) was applied � � b �� x � � y � b � � b � x � � b � x � � b �� x � x � �b �� x �

  10. 3D Surface plots: Maximal SCFA Production 3D Surface plots: Maximal SCFA Production Efficiency and Percentage of Propionic Acid Efficiency and Percentage of Propionic Acid 40,0 280 %HPr on SCFAs 240 30,0 SCFAs Efficiency (mgCOD/gVSS) 200 20,0 160 120 10,0 80 0,0 40 0 5,5 5,5 7,0 7,0 8,5 8,5 23.75 23.75 Initial pH 10,0 10,0 Initial pH Ratio COD/N Ratio COD/N 18.75 18.75 0,0 ‐ 10,0 10,0 ‐ 20,0 20,0 ‐ 30,0 30,0 ‐ 40,0 120 ‐ 160 160 ‐ 200 200 ‐ 240 240 ‐ 280 Low initial pH & higher fraction of PS Initial fermentation pH<8.5 & higher fraction of PS promote highest % HPr favoured the production of the SCFA

  11. 3D Surface Plots: P Released and Percentage of P 3D Surface Plots: P Released and Percentage of P Recovered Recovered %PO4 ‐ P recovered (mgP/gVSS) PO4 ‐ P release (mgP/gVSS) 10,0 100 8,0 75 6,0 50 4,0 25 2,0 0 0,0 5,5 5,5 7,0 7,0 8,5 23.75 8,5 Initial pH 10,0 Initial pH 23.75 Ratio COD/N 10,0 18.75 Ratio COD/N 18.75 0,0 ‐ 2,0 2,0 ‐ 4,0 4,0 ‐ 6,0 0 ‐ 25 25 ‐ 50 50 ‐ 75 75 ‐ 100 Increase of PO 4 ‐ P release observed at higher Higher PO 4 ‐ P recovery noted at low initial initial pH pH & higher fraction of WAS

  12. SBFR: SCFA Production SBFR: SCFA Production Yield of Propionic Acid Yield of Propionic Acid Sludge COD/N Period Initial fermentation pH Type (gCOD/gN) I WAS 26.6 8.5 II PS&WAS 21.8 5.76 (Uncontrolled) III PS 18.7 6.19 (Uncontrolled) 9,00 140,0 PERIOD I (WAS) PERIOD II (WAS+PS) PERIOD III (PS) Propionate production 8,00 120,0 7,00 (mgCOD/gVSS) 100,0 6,00 5,00 80,0 pH 4,00 60,0 3,00 40,0 2,00 20,0 1,00 0,0 0,00 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 Time (d) Yield of propionate pH effluent

  13. SBFR: SCFAs Composition SBFR: SCFAs Composition Acetic acid/ Propionic acid (HPr/HAc) Acetic acid/ Propionic acid (HPr/HAc) PERIOD I PERIOD II PERIOD III 1,8 WAS PS WAS+PS HPr/ HAc (gCOD/ gCOD) 1,6 1,4 1,2 1,0 0,8 0,6 0,4 0,2 0,0 0 10 20 30 40 50 60 70 Time (d)

  14. 3 ‐ Release & Recovery by Struvite Crystallization. 3 ‐ Release & Recovery by Struvite Crystallization. SSFL: PO 4 SSFL: PO 4 3 ‐ ‐ P released 3 ‐ ‐ P recovered PO 4 Final PO 4 % PO 4 ‐ P recovered (mgP/gVSS) (mgP/gVSS) 2.11 1.43 WAS 55.0 PS+WAS 1.27 1.22 96.0 PS 0.96 0.85 89.0 89 % 55% 96 % PS+WAS PS Recovery WAS Recovery Recovery 1,4 1 2,4 1,2 2 0,8 3 ‐ ‐ P/gVSS) 3 ‐ ‐ P/gVSS) 3 ‐ ‐ P/gVSS) 1 1,6 0,6 0,8 1,2 (mgPO 4 (mgPO 4 (mgPO 4 0,6 0,4 0,8 0,4 0,2 0,4 0,2 0 0 0 Before After Before After Before After

  15. Conclusions Conclusions Fermentation of sewage sludge provide a suitable source of SCFAs and • 3— P for a wide range of applications ; PO 4 • The sewage sludge type and the initial fermentation pH affect the production and composition of SCFA; • Higher production of Propionic acid was observed at an initial fermentation pH in a range between 5.5 ‐ 8 and with higher fraction of PS (high COD/N ratio); • The alkaline fermentation of WAS enhanced the release of nutrients (N and P), which can be recovered by struvite crystallization up to 11 mg Struvite/gVSS.

  16. Phosphorus recovery and VFAs production from sewage sludge fermentation Natalia Herrero García Thank you for your attention D. Crutchik, N. Frison, A. Jelic and F. Fatone

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