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Technical Options of Phosphorus Removal in

Wastewater Treatment plant (WWTP)

M. Barjenbruch, E. Exner
FG Siedlungswasserwirtschaft, TU Berlin
Gustav-Meyer-Allee 25, D - 13355 Berlin
Phone: +49 / (0) 30 / 314 72246; Fax: +49 / (0) 30 / 314 72248
e-mail: matthias.barjenbruch@tu-berlin.de, e.exner@tu-berlin.de

Importance of phosphorus
12. frequent element of the crust of earth
Phosphorus is a chemical element. Symbol P
ordinal number 15 and has a specific weight of 31 g/mol
Greek - lichttragend, given by the shining of the white
phosphorus in the reaction with oxygen.
P was discovered in 1669 by Hennig Brand, a German pharmacist
and alchemist.
Phosphorus is essential important for all organism.
P-compounds are parts of DNA- and RNA-molecules
The phosphorus containing compounds ADP/ATP are playing and
important parts in the energy metabolism of all cells.

A man with 70 kg contains about 700 g phosphorus, from which 600 g


is bound in the bones
Important nutrient for the growth of plants and essential fertilizer
Main resources come from: Morocco, South Africa, Russia, China and
USA
Resource remain only according WHO only about 60-80 years

Objectives of the P-elimination


Prevention of the eutrophication of water bodies. P effects in water bodies
eutrophication already in the lower range of microgram especially in:

Lakes, dammed or tide influenced water bodies, Northern Sea of Baltic Sea
Factor of minimum for the growth of plants: N : P = 7:1.
Classification of lakes:
Eutrophic; nutrient rich lakes, in depth about 0-30%,
O2-saturation, only 2 m sight in depth, high production of algae,
tot. P~ 45 - 85 g/l
River according the German Surface water ordinance
g P/l large rivers in the middle mountain; inlets to the Baltic Sea
50
50/100 g P/l all other rivers
Surveillance value of WWTP according wastewater ordinance
10,000 - < 100,000 PE: 2.0 mg P/l

> 100,000 PE: 1.0 mg P/l


Special regional restrictions!

Examples of Eutrophication

Origin and estimation of the specific P-load in municipal


sewage [in g P / (Ed)]
Origin of phosphorus

1975

2005

Metabolism products1)

1,6

1,6

Washing powder for textiles

2,252)

05)

Household detergents/washing-up liquid

0,752)

0,246)

Other P-sources3)

0,42)

0,054)

Sum, related to PE

5,0

1,9

Industry/trade/settlement aeras (as PE)

1,28)

1,27)

Average Concentration (mg/l)9)

15,7

6,9

Concentration in Germany: 5,6 - 14 mg P/l

Phosphorus in the sewage


Main part of the total phosphorus (ca. 68%):
In an inorganic solved status, mainly orthophosphate and
possible condensed phosphates

Smaller part of the total phosphorus:


organic solved and none solved mode (phosphonate, hardly
degradable organic P-compounds from textile industry and
from heat-/power-production)

Condensed and organic parts of phosphorus will mainly


tranfered into ortho phosphates
Only ortho phosphate can be removed from the water
by precipitation and following separation!

Processes of phosphorus elimination


Phosphorus can not be transferred like as nitrogen into the
gaseous status and eliminated to the air.
Phosphorus compounds must be removed from the wastewater in
a stable (solid) aggregated status bounded in separateble particles
via the sludge path.
Processes of chemical P-elimination
Me3+ + PO43- Me(PO)4 + Me (OH) metals: Fe3+, Al3+
Pre-, simultaneous- and final pr, Nachfllung, or combination
precipitation
Influence parameters for the efficiency of the precipitation
Dosage
-relation factor
pH-value
Ca2+
Particle separation

Processes of biological P-elimination (Bio-P)


Combination of Bio-P and chemical P-elimination

Processes of the chemical P-elimination


Pre-precipitation
= 2-3

CPe

PA
SF

Simultaneous
precipitation
= 1,2 1,5

Combined
precipitation

PA
PS

PA: preciptation agent

PA
AT

SS

PA
PA SS

= 1,2 1,5

PA PA
PS

TF/AT

PS

AT

2 mg/l

1-1,5 mg/l
z.T. < 1,0

= 2 2,5

PA

PA
SS

CF

< 0,5 mg/l


= 0,3 mg/l

Calculation of the amount of the precipitant


-value: relative amount of precipitant with the unit [mol Me/mol XP,Prec]
prec

X Me / AM Me

X P , Fll / AM P

with:
XMe
XP,Fll

[mol Me / mol P ]

= 1,0 stochiometric dosage


= 1,5 50 % over stochiometric dosage

necessary amount of precipitant (metal) (mg Me/l sewage),


phosphorus to be precipitated (mg P/l sewage),
X P , prec C P , In C P ,out X P , BM XP , DN X P , BioP

AMMe
atomic mass of metal (mg/mmol),
AMP
atomic mass of phosphors (mg/mmol)
and the atomic mass AM: (P) Phosphor: 31; (Fe) iron 56 ; (Al) aluminium 27
According the kind of bounded P in the sludge:
= 1,0 % (nitrification, COD Elimination)
XPBM
XPBDN = 0,5 % (denitrification)
XPBioP = 1,0 % (anaerobic tank)

Concurrent reactions
Parallel to the precipitation reaction several concurrent
reactions appear:
Hydroxyd development
Me3+ + 3OH- Me(OH)3

Carbonate development
Ca2+ + CO32- CaCO3

Komplexierung of organic substance


Different reaction of adsorption

Follow ups of by-reaction


Higher consumption of precipitation agent
Increase of the sludge production

Amount of additional sludge


The phosphate, hydroxides and all other flucculated
compounds formed by the precipitation agents produce
a higher amount of sludge (Dry solids (DS))
2,5 g DS/g Fe (about 5,0 g DS/g P),
4

g DS/g Al (about 4,0 g DS/g P).

If you apply calcium products you have to calculate with


1.35 amount of flocculant as an increase of sludge:
pH-value at 9,5 about 50 g DS/(PE d),
pH-value at 11 about 200 g DS/(PE d).

Theses additional amounts of sludge have be regarded


in the planning of the sludge treatment process!

Jar-tests with iron-(III)-chloride


Example

-value

1,2

2,0

2,8

3,6

Common precipitants
Product description

aluminium chloride

Iron (III)-chloride

Iron (III)-chloridsulphate

iron(II)-sulphate

Sodium aluminate

Chemical formu

AlCl3

FeCl3

FeClSO4

FeSO4 7 H2O

NaAl(OH)4

Calciumhydroxid
White lime hydrate
(extinguihedr lime)
stabilisied lime milkj
(20 %ig)

Ca(OH)2

polyaluminium-(hydroxid)chloride (PAC)

[Al(OH)3-xClx]n

typical
delivery form
density or
bulk density
[t/m3]

storage and
dosage

effective kation
for
P-precipitation

dilution
1,3

reservoir
acid-resitent pump

Al3+

dilution
1,41 1,43

reservoir
acid-resitent pump

Fe3+

dilution
1,43 1,52

reservoir
acid-resitent pump

Fe3+

residual damp
(green-) salt
1

Einsumpfbunker
acid-resitent pump

Fe2+ Fe3+

dilution
1,3 1,5

reservoir
pump

Al3+

powder
0,45
suspension
1,15

Silo
Schnecke
Tank
Exzenterpumpe

Ca2+

dilution
1,2 1,37

Al3+
reservoir
acid-resitent pump

According DWA 2011

common
active substances
per kg
delivery form

pH
from
(saturated)
dilution

58 60 g/kg
2,2 mol/kg

135 138 g/kg


2,4 2,5 mol/kg

123 g/kg
2,2 mol/kg

178 195 g/kg


3,2 3,5 mol/kg

62 105 g/kg
2,3 3,9 mol/kg
376 g/kg
9,4 mol/kg
75 g/kg
1,9 mol/kg
70 90 g/kg
2,6 3,3 mol/kg

14

12,5

13

Requirements on the an die pureness of


the flocculation agent
Parameter

[mg/mol ESMe]

Lead (Pb)

15

Cadmium (Cd)

0,2

Chromium (Cr)

15

Copper (Cu)

15

Nickel (Ni)

20

Mercury (Hg)

0,15

Zinc (Zn)

50

AOX

Guidance values in flocculation agents to protect the


environment against heavy metal discharge
According DWA 2011

Dosage of the precipitation agent


at locations with by flow increase turbulence
in short distance of the storage tank
Protection pipe

hydraulic direct jump


Increase of the cross section,
absorption chamber of weirs,
Drop construction
junction of part flows
Installation of mixer with a high frequency
Installation of screens and static mixers
Archimedes screw (e.g. filtration)
Pressure side turbulence of pumps
Aerated flow section

(Fe2+)

Example of good location for the dosage of


precipitations agents

Precipitation agent

blast pipe
Sewage

Cnannel

Venturi

Flow breaker

Break, bend

Examples of location for dosage

Bad solution

good solution

bad mixing of the flocculant


durch Randlage kaum B nearly no
contact to the complete water surface

Dosage into the change of flow direction


but better would be over the whole
cross-section

Examples of location for dosage

Good mixing conditions


special injections form different side of
the pipe
Against the flow direction

also good mixing conditions


but danger of corrosion

Storage of the flocculation agent


Sealed filling place
Separated catchment of
losses of the flocculation
agent

Principle of the enhanced biological P-elimination

B
ANAEROBIC
P-Release

PO4 -P

AEROBIC
P-Up-take

luxery uptake
C

Time

Biological P-elimination
Advantages:
No additional agents (flocculants) necessary
Decrease of salts in the effluent of a WWTP
Lower additional sludge production
No additional heavy metals in the sludge
No disturbances possible for the nitrification process

Disadvantages
Higher investment cost for the construction
of the anaerobic tank
A little bit more instable process, so often additional chemical dosage
is required
In winter time higher tendency of bulking sludge

Dimensioning
Contact time and Detention time
Detention time
tR =

VAN
QIn

Contact time
tc =

VAN
(Qrs + Q In)

Dimensioning (biological P-elimination) DWA A 131


anaerobic tank: > 0,5 to 0,75 h
Regarding the maximum dry weather flow and the flow of the
return sludge

Bio-P
Phoredox-process (Detention time: 0,5 to 0,75 h)
aerated zone
anaerobic anoxic zone
zone denitrification COD-elimination
& nitrification

Inlet

= 1,2 1,5
PA

CPe
1-1,5
mg/l
2,0 mg/l
z.T. < 1,0
Effluent

Aeration
Internal recirculation

Secondary Settler

Return sludge

Excess Sludge

Example
WWTP Lbeck-Priwall

Modified-UCT-Process

Anaerobic Anoxic zone


aerated zone
zone denitrification COD-elimination &
Nitrification

Inlet

effluent

Aeration
interanl recirculation

Secondary
settler

Return slduge

Excess sludge

ISAH-process

Inlet

Anaerobic Anoxic zone


Aerated zone
zone
denitrification COD-elimination
& nitrification

Return
sludge
Denitrifcation

Effluent

Aeration
Internal recirculation

Secondary
Settler

Return sludge

Excess Sludge

P-elimination in Germany and DWA North-East


Ptot- mean values in WWTP effluent 1992 to 2009

Ptot-Effluent
values
Pges.-Ablaufwert
[mg/L] [mg/l]

4
3,5

3,5

Inlet:
14 5.6 mg P/l

3
2,5
2

1,70

1,5

2,4

1
0,5

Effluent:
1.0 0.49 mg P/l

1,20
1,00

Pges.Abl-Nord-Ost

2,4

1,70

1,00

Pges.-Abl. D[mg/L]

0,90

1,00

0,90

0,80 0,80 0,80


0,80 0,80
0,80 0,78 0,75
0,75 0,75
0,8
0,8
0,76
0,75
0,7
0,64
0,64 0,66
0,63 0,67 0,63

0
1992 1993 1994 1995 1996 1997 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007 2008 2009

DWA, 2010

Year
Jahr

Effects of PA-consumption on Ptot-effluent


with lower Ptot-Effluent value higher amount of precipitant is needed
60
CP,AN 0,5 mg/l

55
50

CP,AN 2,0 mg/l


10

73

45

KP [mol Me/kg P]

CP,AN 1,0 mg/l

15

107

40

14
44

35
30
25
20

26

38
14

15
10
5
0
Bio-P

Deni

Chem-P

Influence of the dosage location


Inlet to activated tank has the highest
floccucation agent demand 20-25%

60
55

Zulauf Biologie

Rcklaufschlamm

50

108

45

KP [mol Me/kg P]

Ablauf Biologie

Mehrfachdosierung
7
13

27

67

40

12

12

35
30
25
20

23

31

11

15
10
5
0
Bio-P

Deni

Chem-P

Thank your
for attention
Bio-P-Becken 1. Biologische Stufe