Lectures Vaccari - Physicochemical Nutrient Recovery Technologies

1. Physicochemical
Nutrient Recovery
Technologies
David A. Vaccari
dvaccari@stevens.edu
Cities of the Future
Lago di Como
May 13, 2016

2. Outline
• Nitrogen removal and recovery
– Stripping and Scrubbing
• Phosphorus precipitation
– Direct precipitation
– Crystallization
• Incinerator ash
– Leaching/extraction
– Thermal
2

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. Ammonia Stripping/Scrubbing
4
NH4
+  NH3 pKa = 9.24
NH4
+ NH3

5. Ammonia Stripping/Scrubbing
(Nitrification must be avoided)
5
NH4
+ NH3
Caustic
Air
H2SO4
NH4SO4
or HNO3
or NH4NO3

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. 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. 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. 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. 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. 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. 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. 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. 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. 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. 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. Current Treatment Technologies
for Point Source Discharge
(Courtesy Chelskey Shepsko & Arun SenGupta
• Electrodialysis / Reverse Osmosis
Source: FuMA-Tech, 2016.

18. WAC and HAIX-Zr Ion Exchange
Process for Removal

19. HAIX-NanoZr Synthesis

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. 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. Some Commercially Available Full-Scale Processes
22
E. Desmidt et al, Phosphorus Scarcity and P-Recovery Techniques (U. Gent, 2014)

23. 23
Mg2+ + NH4
+ + PO4
3- MgNH4PO4∙6H2O
Accidental Struvite Formation
(courtesy of Michael Ditton, Ostara Co.)

24. 24
Fluidized Bed Struvite Precipitation

25. 25
Phosphorus Recovery Intercepts Recycle to
Recover Phosphorus and Ammonia
(courtesy of Michael Ditton, Ostara Co.)

26. 26
WASSTRIP Increases P Recovery while protecting
Digesters from Struvite Formation
(courtesy of Michael Ditton, Ostara Co.)

27. 27
Crystalized Struvite Product
(courtesy of Michael Ditton, Ostara Co.)

28. Ostara Pearl®
STRUVITE PRECIPITATION ALTERNATIVES
Multiform
Harvest
Kansas
Environmental
Management
Associates
(KEMA)
Phred™

29. Crystallactor
29

30. Incinerator Ash
Vlasta Klima Balloun Lecture

31. Seaborne Process
Recovery of P and N; Removal of Heavy Metals
Energy Recovery by Incineration of Biosolids
31

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. 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. 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. What do you think?
David A. Vaccari dvaccari@stevens.edu