Phosphorous removal by

physicochemical and
biological means
Dr. Mathias Ernst
Technische Universitt Berlin
Head of Centre for Water in Urban Areas
1

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 (%)

< 25 mg/l
70-90

COD (mg/L)
Removal rate (%)

< 125
75

SS
removal rate [%]

< 35
90

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

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

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

<2
<1

Implementaion in Germany
Wastewater ordinance (AbwV)
Parameter

Class 1

Class 2

Class 3

Class 4

Class 5

Ruhleben

BOD5 (mg/L)

40

25

20

20

15

COD (mg/L)

150

110

90

90

75

45

NH4-N (mg/l)

10

10

10

0.3

Nitrogen, N-total
(Kjeldahl) (mg/l)

10

18

13

Phosphorus, total
(mg/l)

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

Relevant for TP removal

Particulate/Colloidal (cell fragments)
Dissolved phosphorous

10, 3, 7 mg/L;

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

Particle Size Removal Efficiency:

III Filtration of Activated Sludge Effluent

10

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

12

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)

14

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)
16

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)

17

Badegewsserrichtlinie

Water management at Berlin

Tegel Lake

Tegel Lake
Area:

4 km

Average depth:

8m

Max depth:

16 m

At its banks:

wells and water work to produce dw from bank filtrate

Three inflows:

Nordgraben (with Panke), Tegeler Flie, Oberhavel

70s:

2.88 mg/L PO43- in Tegel Lake

1985:

p-elimination plant put into operation, capacity 6 m3/s

2003:

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

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)

26

Enhanced biological Phosphorous Removal

Review: C and N removal two stages

External Carbon Source

QE

QI

N - Aerobic
NH4 ~> NO3
BOD5 ~> CO2

DN - Anoxic
NO3 ~> N2

QR (Return Activated Sludge)

QR
QW

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

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

org C + O2 ~> CO2

org C + NO3 ~> CO2 + N2

27

Review: C and N removal one stage

QE

QI

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

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

org C + O2 ~> CO2

org C + NO3 ~> CO2 + N2

28

Review: C and N removal one stage

max. 80 % N-Removal

QI 100 l/s

500 l/s

DN - Anoxic
NO3 ~> N2
300 l/s

QIR

100 l/s

QR

N - Aerobic
NH4 ~> NO3
BOD5 ~> CO2

100 l/s
QE

QW
O2
BOD5
NH4
NO3

29

Enhanced biological Phosphorous Removal

QI

QE
Anae

PO4
Rel.

DN - Anoxic
NO3 ~> N2

N - Aerobic
NH4 ~> NO3
PO4 Uptake

QIR
QR

QW
Autotroph B. (aerobic)
Heterotroph B.
BOD5 Removal (aerobic)
Denitrification
Denitirfication(anoxic)
(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

N - Aerobic
NH4 ~> NO3
PO4 Uptake

QE

QIR
QR

QW
O2
NO3
BOD5
PO4

31

Enhanced biological Phosphorous Removal

QE

QI
Anae

PO4
rel.

DN - Anoxic
NO3 ~> N2

N - Aerobic
NH4 ~> NO3
PO4 Uptake

QIR
QR
QW

Optional: Al3+ Fe3+ salts

32

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)

33

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)
34

Thank you for your attention !

Mathias.ernst@tu-berlin.de