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Phosphorous removal by physicochemical and biological means

Dr. Mathias Ernst


Technische Universitt Berlin Head of Centre for Water in Urban Areas
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Outline

EU and German wastewater legislation Relevant phosphorous compounds Physico-chemical removal methods Surface water treatment plant Tegel (Berlin) Enhanced biological P removal process Conclusion

European Requirements 91/271/EEC municipal wastewater


Sensitive waters
BOD5 (mg/L) Removal rate (%) COD (mg/L) Removal rate (%) SS removal rate [%] < 25 mg/l 70-90 < 125 75 < 35 90

Nitrogen TNl (mg/l) 10.000-100.000 P.E >100.000 P.E.


Phosphorus TP (mg/l) 10.000 - 100.000 P.E. >100.000 P.E.

< 15 (70-80%) < 10 (70-80%)

<2 <1

Implementaion in Germany Wastewater ordinance (AbwV)


Parameter Class 1 Class 2 Class 3 Class 4 Class 5 Ruhleben 4 45 0.3 8 BOD5 (mg/L) COD (mg/L) NH4-N (mg/l) Nitrogen, N-total (Kjeldahl) (mg/l) Phosphorus, total (mg/l) 40 150 25 110 20 90 10 10 20 90 10 18 15 75 10 13

0.2

Class Class Class Class Class

1: 2: 3: 4: 5:

<40 kg BOD5/d 40-200 200-400 400-4000 >4000


1 P.E.= 60 g BOD5/d

Typical Concentrations of Total Phosphorus in Water

Domestic wastewater 3 15 mg/L TP Table 6-4

Agricultural drainage 0.05 1 mg/L TP


Mesotropher Bereich TP 14.5 - 49 mg m-3 Chl a 3 - 7.4 mg m-3

Lake surface water 0.01 0.04 mg/L TP

[Vollenweider, 1982]

Forms of Phosphorus

Total P (TP) consists of Total organic P (TOP) (e.g., phospholipids), Total inorganic P (TIP) (ortho- and poly-phosphates);
Raw wastewater: TP, TOP, TIP 10, 3, 7 mg/L;

Phosphoric acid system

Forms of Phosphorus

Total P (TP) consists of Total organic P (TOP) (e.g., phospholipids), Total inorganic P (TIP) (ortho- and poly-phosphates);
Raw WW: TP, TOP, TIP 10, 3, 7 mg/L;

Relevant for TP removal Particulate/Colloidal (cell fragments) Dissolved phosphorous

Rapid Sand Filtration (RSF): a DW technology applied to AWWT (III Filtration)

Single media (sand or anthracite) vs. Multi Media (sand and anthracite); (sand and granular active carbon)
Particle size < 0.5 mm up to > 2 mm
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Particle Size Removal Efficiency: III Filtration of Activated Sludge Effluent

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III- Filtration with Chemical Addition

Chemicals Added:
Metal coagulants (Al(III), Fe(III)), organic polymers, lime

Metal Coagulants:
Al3+ (or Fe3+) + 3 OHAl(OH)3 (or Fe(OH)3 ) In AWT, generally operate in sweep flock Also Al3+ (or Fe3+) + PO43AlPO4 (or FePO4 ); Al:P (molar): 1.4, 1.7, 2.3 75 %, 85 %, 95 % P removal

Log C vs. pH Diagram: Equilibrium Phosphate and Aluminum Concentrations

Figure 6-13

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Lg c(Al, Fe) vs. pH (Al-, Fe-Hydroxids)

Stabilittsdiagramm fr Eisen und Aluminium

III- Filtration with Chemical Addition

Chemicals Added:
Metal coagulants (Al(III), Fe(III)), organic polymers, lime

Metal Coagulants:
Al3+ (or Fe3+) + 3 OHAl(OH)3 (or Fe(OH)3 ) In AWT, generally operate in sweep flock Al3+ (or Fe3+) + PO43AlPO4 (or FePO4 ); Al:P (molar): 1.4, 1.7, 2.3 75 %, 85 %, 95 % P removal

Organic Polymers:
Primary coagulants (cationic, anionic, non-charged polymers)

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Polymer flocculation

Highmolecular compounds adsorb on two particles Highmolecular polymers (0, +, -) as flocculation aid

III- Filtration with Chemical Addition

Chemicals Added:
Metal coagulants (Al(III), Fe(III)), organic polymers, lime

Metal Coagulants:
Al3+ (or Fe3+) + 3 OHAl(OH)3 (or Fe(OH)3 ) In AWT, generally operate in sweep flock Al3+ (or Fe3+) + PO43AlPO4 (or FePO4 ); Al:P (molar): 1.4, 1.7, 2.3 75 %, 85 %, 95 % P removal

Organic Polymers:
Primary coagulants (cationic, anionic, non-charged polymers)

Lime (Ca(OH)2

Ca2+ + 2 OH-):

Ca2+ + CO32CaCO3 Mg2+ + 2 OHMg(OH)2 3 Ca2+ + 2 PO43Ca3(PO4)2 5 Ca2+ + 3 PO43- + OHCa5(PO4)3OH

(hydroxyapatite)
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III- Filtration with Chemical Addition

Point of application for P removal :

III-Filtration relatively low doses; In-Line, Static Mixer, Rapid Mixer or Flocculator

Before I-Sedimentation (High Doses); Before Biological Process (interaction with biology); Before II-Sedimentation (Higher Doses)

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Badegewsserrichtlinie

Water management at Berlin

Tegel Lake

Tegel Lake
Area: Average depth: 4 km 8m

Max depth:

16 m

At its banks: Three inflows: 70s: 1985: 2003:

wells and water work to produce dw from bank filtrate Nordgraben (with Panke), Tegeler Flie, Oberhavel 2.88 mg/L PO43- in Tegel Lake p-elimination plant put into operation, capacity 6 m3/s 0.05 mg/L PO43- in Tegel Lake

two pipes: DN 1000 each flocculant: Fe2(SO4)3 Fe3+ + PO43- FePO4 pH=5-5.5

Fe3+ + 3 OH- Fe(OH)3 pH 8 - 9 coagulation (destabilisation, microflocs: 0.01 - 0.05 mm)

complexation with organic compounds


adsorption reactions residual time 30 s (time for coagulation) pipe flocculation -factor:

PO4

cFe cPO4

Addition of flocculation aid: weak anionic polyacrylamide macroflocs: agglomeration faster, bigger sink faster

Sedimentation and Filtration


Processes
B C Sedimentation Post-precipitation, coagulation, and -flocculation Filtration

Double bed filter: pumice stone / sand Backwash every 24h

Phosphate elimination plant Tegel

Feed concentration 0.2 0.5 mg/L TP (mixture of three feed waters) Effluent: 18-22 g TP/L (required: 25 g TP/L) P-removal of 96% - 99% Present costs of treatment: 7 cent/m (incl. depreciation)

Green: class II Yellow: class III

Tegel Lake
Water quality class II
Other waters in Berlin: Class II-III or Class III

Second P removal plant in Berlin: Chain of the Grunewald lakes (drinking water assurance)

III- Filtration with Chemical Addition

Clarification / Sedimentation before filtration if high doses Performance: Up to 95 % P removal; turbidity 1 NTU Other benefits of chemical clarification: 1) High-Ph disinfection by lime; 2) Physical removal of pathogens by III Filtration; Enhanced microbial removals: >2-log protozoa and bacteria; >1-log viruses 3) Chemical precipitation of metals (e.g., Zn(OH)2 , or adsorption onto Al(OH)3 flock) (flock sweep effect)

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Enhanced biological Phosphorous Removal


Review: C and N removal two stages

External Carbon Source


QI QE

N - Aerobic NH4 ~> NO3 BOD5 ~> CO2

DN - Anoxic NO3 ~> N2

QR (Return Activated Sludge)


QW

QR
QW

Autotroph B. (aerobic) Heterotroph B. BOD5 Removal (aerobic) org C (BOD) ~> org C (Biomass) Denitirfication (anoxic) org C (BOD) ~> org C (Biomass) Denitrification (anoxic)

C-Source Energy-Source inorg C (CO2) ~> org C (Biomass) NH4 + O2 ~> NO3 org C + O2 ~> CO2 org C + NO3 ~> CO2 + N2
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Review: C and N removal one stage


QI QE

DN - Anoxic NO3 ~> N2

N - Aerobic NH4 ~> NO3 BOD5 ~> CO2

QIR (Internal Recirculation) QR (Return Activated Sludge) QW


C-Source Energy-Source inorg C (CO2) ~> org C (Biomass) NH4 + O2 ~> NO3 org C + O2 ~> CO2 org C + NO3 ~> CO2 + N2

Autotroph B. (aerobic) Heterotroph B. BOD5 Removal (aerobic) org C (BOD) ~> org C (Biomass) Denitrification (anoxic) Denitirfication (anoxic) org C (BOD) ~> org C (Biomass)

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Review: C and N removal one stage


max. 80 % N-Removal 500 l/s 100 l/s QE

QI 100 l/s

DN - Anoxic NO3 ~> N2


300 l/s 100 l/s O2 BOD5 NH4 NO3
QIR QR

N - Aerobic NH4 ~> NO3 BOD5 ~> CO2

QW

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Enhanced biological Phosphorous Removal


QI QE
Anae

PO4 Rel.

DN - Anoxic NO3 ~> N2 QIR QR

N - Aerobic NH4 ~> NO3 PO4 Uptake

QW
Autotroph B. (aerobic) Heterotroph B. BOD5 Removal (aerobic) Denitrification (anoxic) Denitirfication (anoxic) PAOs Step 1 (mainly anaerobic) Step 2 (mainly aerobic, anoxic) C-Source Energy-Source inorg C (CO2) ~> org C (Biomass) NH4 + O2 ~> NO3 org C (BOD) ~> org C (Biomass) org C (BOD) ~> org C (Biomass) Storage Consumption org C ~> Intrac. C growth on In. C org C + O2 ~> CO2 org C + NO3 ~> CO2 + N2 Storage Consumption Poly-P ~> PO4 PO4 ~> Poly-P Cons. of In. C 30

Enhanced biological Phosphorous Removal


QI
Anae

PO4 Rel.

DN - Anoxic NO3 ~> N2


QIR
QR

N - Aerobic NH4 ~> NO3 PO4 Uptake

QE

QW O2 NO3 BOD5 PO4


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Enhanced biological Phosphorous Removal

QI
Anae

QE
PO4 rel.

DN - Anoxic NO3 ~> N2


QIR QR

N - Aerobic NH4 ~> NO3 PO4 Uptake

QW

Optional: Al3+ Fe3+ salts


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Advantages of EBPR

Only slight increase of waste sludge production as P is stored intracellular Less chemical precipitation necessary Reduced chemical demand Reduced waste sludge production in comparison with chemical removal only Only small anaerobic volumes necessary (option for retrofitting possible)

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Conclusions

P removal of municipal wastewaters is necessary to avoid eutrophication in receiving surface waters Required P removal rates are high (up to 99%) as concentrations > 50g/L TP already cause eutrophication in freshwater Physico-chemical P removal requires effective coagulants (Fe, Al, lime, polymers), subsequent tertiary filtration and pH control P/C methods produce considerable amounts of sludge waste EBPR shall be applied where ever appropriate (lower sludge production, higher cost effectiveness, combination with C and N removal)
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Thank you for your attention !

Mathias.ernst@tu-berlin.de