GERMAN ATV-DVWK

RULES AND STANDARDS

Standard
ATV-DVWK-A 202E

Chemical-Physical Methods for the

Removal of Phosphorus from
Wastewater

April 2004
ISBN 3-937758-55-0

Publisher/marketing:
ATV-DVWK German Association for Water, Wastewater
and Waste,
Theodor-Heuss-Allee 17 y D-53773 Hennef
Tel. ++49-22 42 / 8 72-120 y Fax:++49 22 42 / 8 72-100
E-Mail: vertrieb@atv.de y Internet: www.atv-dvwk.de
ATV-DVWK-A 202E

The German Association for Water, Wastewater and Waste, ATV-DVWK, is the spokesman in Germany for
all universal questions on water and is involved intensively in the development of secure and sustainable
water management. As politically and economically independent organisation it operates specifically in the
areas of water management, wastewater, waste and soil protection.

In Europe the ATV-DVWK is the association in this field with the greatest number of members and, due to
its specialist competence it holds a special position with regard to standardisation, professional training and
information of the public. The ca. 15,000 members represent the experts and executive personnel from
municipalities, universities, engineer offices, authorities and businesses.

The emphasis of its activities is on the elaboration and updating of a common set of technical rules and
standards and with collaboration with the creation of technical standard specifications at the national and
international levels. To this belong not only the technical-scientific subjects but also economical and legal
demands of environmental protection and protection of bodies of waters.

Imprint

Publisher/marketing: Setting and printing [German original]:

ATV-DVWK German Association for DCM, Meckenheim

Water, Wastewater and Waste
Theodor-Heuss-Allee 17
D-53773 Hennef
Tel.: +49 (0) 22 42 / 8 72-120 ISBN:
Fax: +49 (0) 22 42 / 8 72-100 3-937758-55-0
E-Mail: vertrieb@atv.de
Internet: www.atv-dvwk.de Printed on 100 % recycling paper

© ATV-DVWK Deutsche Vereinigung für Wasserwirtschaft, Abwasser und Abfall e. V., Hennef 2004

All rights in particular the translation into other languages, are reserved. No part of this Standard may be reproduced in any form – by
photocopy, microfilm or any other process - or transferred into a language usable in a machine, in particular data processing ma-
chines, without the written approval of the publisher.

The scientific correctness of the texts, diagrams and tables does not fall under the responsibility of the publisher.

2 April 2004
 ATV-DVWK-A 202E

Foreword
The first edition of Standard A 202 “Methods for the Removal of Phosphorus from Wastewater” [Not avail-
able in English], which was elaborated by the then ATV Specialist Committee 2.8 “Advanced Treatment of
Wastewater following Biological Treatment”, was published in 1992. Through wide application, in particular
of the chemical precipitation/flocculation, further knowledge was elaborated and experiences gathered
which made it appear to be sensible to revise Standard ATV-A 202. The revised edition is now presented
here.

As a result of the legally laid down limitation of phosphates in detergents in the middle of the seventies and
the extensive introduction of P-removal in municipal wastewater treatment plants since the end of the eight-
ies of the last century, the loading of surface waters from municipal sources has reduced by some 80 %.
Today’s contribution by wastewater treatment plants is ca. 30 % and can be most easily further reduced as
point source. Today’s loading of surface waters originates primarily from diffuse sources and from com-
bined wastewater overflow facilities.

Authors
This Standard was elaborated by the ATV-DVWK Specialist Committee KA-8 “Methods of Advanced Treat-
ment following Biological Treatment”.

The following members belong to the ATV-DVWK Specialist Committee:

Dr.-Ing. Matthias Barjenbruch, Rostock
Dipl.-Ing. Detlef Burkhardt, München
Dr.-Ing. Wolfgang Firk, Düren
Prof. Dr.-Ing. Werner Hegemann, Berlin (Chairman)
Dipl.-Ing. Bernhard Jost, Zürich
Dr.-Ing. Hermann Meyer, Bochum
Dr.-Ing. Anton Peter-Fröhlich, Berlin
Prof. Dr.-Ing. Hermann Johannes Pöpel, Darmstadt
Dr.-Ing. Manfred Roth, Stuttgart
Dr.-Ing. E. h. BD Peter Schleypen, München

The following members of the ATV-DVWK Working Group KA-8.2 “Methods of Advanced Treatment of
Wastewater following Biological Treatment” have collaborated as guests:
Dr.-Ing. Langer, Darmstadt
Dipl.-Ing. Scheffer, Leverkusen

April 2004 3
ATV-DVWK-A 202E

Contents

Foreword.............................................................................................................................................................3

Authors .............................................................................................................................................................3

User Notes ..........................................................................................................................................................5

1 Area of application............................................................................................................................5

2 Definitions and Symbols..................................................................................................................5

3 General Principles of Chemical-Physical Phosphate Removal..................................................7

3.1 Phosphorus Compounds and Phosphorus Loads in Wastewater............................................. 7
3.2 Description of the Procedures using Chemical-Physical Phosphate Removal......................... 7
3.3 Precipitants................................................................................................................................ 7
3.4 Chemical Reactions .................................................................................................................. 9
3.4.1 Precipitation Reaction ............................................................................................................... 9
3.4.2 Competing Reactions ................................................................................................................ 9
3.5 Type of and Requirement for Precipitants................................................................................. 10
3.6 Influencing Factors on Precipitation .......................................................................................... 11
3.6.1 pH Value.................................................................................................................................... 11
3.6.2 Alkalinity .................................................................................................................................... 11
3.6.3 Further Chemical Influencing Variables .................................................................................... 11
3.6.4 Physical Influencing Variables................................................................................................... 11
3.6.5 Influence of the Biological Phase on the Precipitant Requirement ........................................... 12
3.7 Storage and Dosing of Precipitants........................................................................................... 12
4 Methods..............................................................................................................................................13
4.1 Pre-precipitation ........................................................................................................................ 13
4.2 Simultaneous Methods.............................................................................................................. 14
4.2.1 Simultaneous Precipitation........................................................................................................ 14
4.2.2 Simultaneous Precipitation for the Supplementing of Biological Phosphate Removal ............. 15
4.3 Downstream Stages .................................................................................................................. 15
4.3.1 Post-precipitation....................................................................................................................... 16
4.3.2 Flocculation Filtration ................................................................................................................ 16
4.4 Two-stage Precipitation............................................................................................................. 16
5 Influence of Precipitation/Flocculation on the treatment of Wastewater and Sludge.............17
5.1 Influence of Phosphate Precipitation on the Biological Processes ........................................... 17
5.2 Influence of Phosphate Precipitation on the Sludge ................................................................. 17
5.2.1 Solid Matter Load ...................................................................................................................... 17
5.2.2 Sludge Volumes ........................................................................................................................ 18
Appendix A Calculation Examples..................................................................................................................19
A.1 Basic elements of calculation .................................................................................................... 19
A.2 Treatment Methods Investigated and Monitoring Values Ptot.................................................... 20
A.3 Load and Dimensioning Assumptions....................................................................................... 20
A.4 Calculations ............................................................................................................................... 21
A.4.1 Calculation of the Phosphorus to be Precipitated ..................................................................... 21
A.4.2 Calculation of the Precipitant Quantities ................................................................................... 22
A 4.3 Calculation of the Increased Yield of Solid Matter .................................................................... 24
Laws, Standard Specifications and Directives..............................................................................................25

Literature.............................................................................................................................................................25
Reference sources.................................................................................................................................... 25

4 April 2004
 ATV-DVWK-A 202E

User Notes

This Standard is the result of honorary, technical-scientific/economic collaboration which has been
achieved in accordance with the principles applicable therefor (statutes, rules of procedure of the ATV-
DVWK and the Standard ATV-DVWK-A 400E). For this, according to precedents, there exists an actual
presumption that it is textually and technically correct and also generally recognised.

The application of this Standard is open to everyone. However, an obligation for application can arise from
legal or administrative regulations, a contract or other legal reason.

This Standard is an important, however, not the sole source of information for correct solutions. With its
application no one avoids responsibility for his own action or for the correct application in specific cases;
this applies in particular for the correct handling of the margins described in the Standard.

1 Area of application 2 Definitions and

Symbols
This Standard is concerned with the removal of
phosphorus from municipal wastewater through The unified system of Standard ATV-DVWK-A
the employment of precipitation/flocculation. For 198E is adopted for all symbols. Accordingly the
respective main term e.g.:
the biological removal of phosphate attention is
drawn to the Standard ATV-DVWK-A 131E. The • Q for volume flow,
combination of biological P-removal using simulta- • C for concentration (homogenised sample),
neous precipitation is dealt with in detail in Section • S for concentration (filtered sample, 0.45 µm
4.2.2. membrane filter),
• X for concentration (filter residue) and
• B for loads
In surface waters phosphorus is usually the limiting
factor for the growth of algae (primary production) Is followed by an index or indices separated by
or can made this most easily using technical commas.
measures.

Symbol Unit Designation

βPrec [βFäll] mol Me/mol XP,Prec Relative quantity of precipitant (Beta value)
ρPS [ρFML] kg/m3 solution Density of the precipitant solution
AMAl g/mol Relative atomic mass of aluminium
AMFe g/mol Relative atomic mass of iron (Fe)
AMP g/mol Relative atomic mass of phosphorus
AMx g/mol Relative atomic mass of a parameters x
Bd,BOD [Bd,BSB] g/(I · d) Inhabitant-specific daily BOD5 load
Bd, PQ [Bd,FM] g/d Mean dosed absolute precipitant quantity per day in delivered form
Bd,P g/(I · d) Inhabitant-specific daily phosphorus load in the homogenised sample as P
Bh,PQ [Bh,FM] g/h Mean dosed absolute precipitant quantity per hour in delivered form
CBOD [CBSB] mg/l Concentration of BOD5 in the homogenised sample
CPS [CFML] kg/m3 Precipitant concentration of a solution using a powder or granulate precipi-
3
tant (kg precipitant/m solution)
CP mg/l Concentration of phosphorus in the homogenised sample as P
CP,aM mg/l Concentration of phosphorus in the homogenised sample as P as annual
mean

April 2004 5
ATV-DVWK-A 202E

Symbol Unit Designation

PEXXX;ZZ I [E] Population equivalents, e.g. for the characterisation of industrial wastewa-
[EGWXXX;ZZ] ter, always with reference parameter and associated inhabitant-specific
load, e.g. PECOD,120, i. e. depending on the parameter, various PE can result
for one operation
PT [EW] I [E] Total number of inhabitants and population equivalents (PT = P + PE),
depending on parameter possibly different PT
P [EZ] I [E] Number of inhabitants
fp - Peak factor to cover peaks in the phosphorus content in the inflow by the
precipitant quantity
PB -, % Phosphorus bonding in the activated sludge as share of the BOD added to
the biological reactor (CBOD,INB)
PBAna -, % Phosphorus bonding in the activated sludge as share of the BOD added to
the biological reactor (CBOD,INB) with existing anaerobic tank or selector
PBBM -, % Phosphorus bonding in the activated sludge as share of the BOD added to
the biological reactor (CBOD,INB) with the degradation of carbon and, possi-
bly, with nitrification
PBDeni -, % Phosphorus bonding in the activated sludge as share of the BOD added to
the biological reactor (CBOD,INB) with denitrification
Qd,PQ [QdFM] l/d Volume flow of the precipitant to be dosed per day
QPQ QFM l/s Volume flow of the precipitant to be dosed
Qh,PQ [Qh,FM] l/h Volume flow of the precipitant to be dosed per hour
QDW,d [QT,d] m3/d Daily dry weather flow
TS [TR] kg/m3 Concentration of total (dry) solids (evaporation residue)
WSd,BioP [ÜSd,BioP] kg/d, g/d Daily sludge production from the biological phosphorus removal (BioP-
waste active sludge) in kg or. g TS per day
WSd,Chem kg/d, g/d Daily sludge production from the chemical phosphorus removal (chemical
[ÜSd,Chem] waste sludge) in kg or. g TS per day
WSd,P [ÜSd,P] kg/d, g/d Daily sludge production from the phosphorus removal (BioP-waste active
sludge + chemical waste active sludge) in kg or g DR per day
Www,d [WS,d] l/(I · d) Inhabitant-specific daily wastewater yield
ASAl [WSAl] kg Al/kg precipitant Aluminium active substance of the precipitant as delivered
ASFe [WSFe] kg Fe/kg precipitant Iron (Fe) active substance of the precipitant as delivered
ASMe [WSMe] kg Me/kg precipitant Metal active substance of the precipitant as delivered
XP,BioP mg/l Phosphorus biologically bonded with biological P-Removal
XP,BM mg/l Phosphorus incorporated in the biomass
XP,Prec [XP,Fäll] mg/l Phosphorus eliminated through precipitation
z kg Me/kg precipitant Interaction coefficient of the precipitant used

Indices for the site and purpose of the sampling (always as last index)

EB [AB] Sample from the effluent of the aeration tank (biological stage), e.g. SNO3,EB
EF [AF] Sample from the effluent of a filter e.g. SNO3,EF
ESST [AN] Sample from the effluent of the secondary settling stage e.g. CBOD,ESST, XSS,ESST
EP [AT] Sample from the effluent of a pond, e.g. SNO3,EP
ED [DB] Sample from the effluent of the denitrification tank, e.g. SNO3,ED
EN [NB] Sample from the effluent of the nitrification stage, e.g. SNO3,EN
RS Sample from the return sludge
WS [ÜS] Sample from the waste (activated) sludge
In [Z] Sample from the inflow to the wastewater treatment plant, e.g. CBOD,IN, XSS,IN
InB [ZB] Sample from the inflow to the biological stage, e.g. CCOD,INB

Other symbols
BM Biomass
PQ [FMM]* Precipitant quantity
SDM [STM] Sludge dry mass
MV [ÜW] Monitoring value

[* Translator’s Note: In the German original it appears that FMM (Fallmittelmenge) is used only as a symbol. Fallmittelmenge as an
index is FM. In English PQ is used to translate both symbol and index.]

6 April 2004
 ATV-DVWK-A 202E

(PO43-) as well as other anions (precipitation reac-

3 General Principles of tion),
Chemical-Physical • destabilisation of the colloides contained in the
Phosphate Removal wastewater and combination into micro-flocs
(coagulation),

• formation of flocs, i.e. formation of easily sepa-

3.1 Phosphorus Compounds and rable macro-flocs from the micro-flocs, With this
Phosphorus Loads in Wastewater suspended solids and colloids, including the or-
ganically bonded phosphorus in the flocs, can
Due to the limitation of phosphates in detergents be incorporated (co-precipitation and co-
the inhabitant-specific phosphorus yield of ca. 1.8 flocculation),
g/(I · d) has reduced. Depending on the wastewa-
• separation of the macro-flocs from the wastewa-
ter produced and the infiltration water component,
ter. Separation can be effected by sedimenta-
phosphorus concentrations from 5 mg/l to 20 mg/l
tion, flotation, filtration or combination of these
result.
processes.
The greater part of the overall phosphorus, to be
The processes taking place with chemical-physical
determined according to EN 1189, is available in
phosphate removal (precipitation) are essentially
inorganically dissolved form and consists essen-
described under the second bullet point, while the
tially of orthophosphate and possibly condensed
physical sub-processes (flocculation and floc sepa-
phosphates. On the other hand, there is a small
ration) are listed under the three subsequent bullet
part of the phosphorus available both organically
points.
dissolved and non-dissolved. To these also belong
phosphonates, less degradable p-compounds which
are employed in the textile industry and in the area
of combined heat and power generation. 3.3 Precipitants
Many types of polyvalent metal ions, following
Condensed phosphates and organic phosphorus
addition to the wastewater, form insoluble com-
fractions are already extensively converted into
pounds with the phosphate ions dissolved therein.
orthophosphate in the sewer network and during
Fe3+, Al3+, Fe2+ und Ca2+ are employed for phosphate
wastewater treatment processes.
precipitation for economic reasons (see Table 1).
Fe2+ can be used successfully only if it is oxidised
Only orthophosphate can be removed from the to Fe3+ in water containing oxygen. In practice, for
wastewater through precipitation using chemical- this, it is dosed into the aerated grit chamber or
physical processes. into the area of the aeration. Then the same re-
sults can be expected as for the application of
Fe3+. The oxygen necessary for the oxidation of
3.2 Description of the Procedures using iron is insignificant for the dimensioning of the
Chemical-Physical Phosphate aeration facilities for the aeration tanks.
Removal
As a result of using metal salts there is an ex-
change of anions in the water. PO43- forms insolu-
The chemical-physical phosphate removal consists ble compounds with the metal ions and is re-
of five consecutive processes: moved; the anions of the precipitant (Cl- or SO42-)
get into the water. The addition of Cl-- or SO42-
• dosing and completely mixing of a precipitant anions can be tolerated.
into the wastewater flow,
Table 1 gives a summary of the precipitants usu-
• forming of particular bonding of the precipitant ally used in the treatment of wastewater.
cations (Fe3+, Al3+, Ca2+) and phosphate anions

April 2004 7
ATV-DVWK-A 202E

Requirements on the purity of precipitants It is to be assumed that the impurities are taken up
The precipitants are in part by-products or waste in the precipitation sludge and appropriately in-
products of industrial processes. In these cases crease the loads in the sewage sludge produced.
impurities such as, for example, heavy metals and With a view to phosphate recycling these impuri-
organic halogen compounds can appear, which ties should as far as possible be avoided.
are conditioned by production or the natural prop-
erties of the initial raw materials.

Table 1: Common precipitants

Chemical Typical Storage and Effective Normal active pH value of the

formula form of delivery dosing cation for p- substance (saturated)
and density or precipita- content in g/kg solution
Product description
bulk weight tion and mol/kg
3
in t/m delivery form

3+
Aluminium chloride AlCl3 Solution Tank Al 58 – 60
1.3 Acid-resistant 2.2 1
pump
3+
Aluminium iron(III) chlo- AlCl3 + FeCl3 Solution Tank Al 19
3+
ride 1.15 Acid resistant Fe 10 1
pump 0.9
3+
Aluminium sulphate Al2(SO4)3 Granulate, po- Silo Al 40
wder Screw 1.5
1
Solution Tank 24 3
1.27 Pump 0.9
3+
Aluminium iron(III - [Al2(SO4)3 + Granulate Silo Al 82
3+
sulphate Fe2(SO4)3] · n H2O 0.95 Screw and Fe 10 2
eccentric pump 3.2

2+ 3+
Iron(II) chloride FeCl2 Solution Tank Fe → Fe 86 – 135
1.24 – 1.37 Acid resistant 1.5 – 2.4 1
pump
3+
Iron(III.-chloride FeCl3 Solution Tank Fe 135 – 138
1.41 – 1.43 Acid resistant 2.4 – 2.5 1
pump
3+
Iron(III) chloride sulphate FeClSO4 Solution Tank Fe 123
1.43 – 1.52 Acid resistant 2.2 1
pump
2+ 3+
Iron(II) sulphate FeSO4 · 7 H2O Residual moistu- Ponding bunker Fe → Fe 178 – 195
re (green) salt Pump 3.2 – 3.5 2
1
2+ 3+
Iron(II) sulphate FeSO4 · n H2O Granulate Silo Fe → Fe 195
0.8 Screw and 3.5 3
eccentric pump
3+
Iron(III) sulphate Fe2(SO4)3 Solution Tank Fe 118
1.5 Acid resistant 2.1 1
pump

Calcium hydroxide Ca(OH)2 Powder Silo 376

2+
White lime hydrate 0.45 Screw Ca 9.4
(slaked lime) Suspension Tank 75
Stabilised milk of lime 1.15 Eccentric pump 1.9 12.5
(20 % by wt.)

3+
Sodium aluminate NaAl(OH)4 Solution Tank Al 62 – 105
1.3 – 1.5 Pump 2.3 – 3.9 14
3+
Polyaluminium (hy- [Al(OH)3-xClx]n Solution Tank Al 70 – 90
droxide) chloride (PAC) 1.2 – 1.37 Acid resistant 2.6 – 3.3 1-3
pump
3+
Polyaluminium- Alx(OH)yClz(SO4)k Solution Tank Al 52 – 90
(hydroxide)-chloride- 1.4 Acid resistant 1
sulphate pump 1.9 – 3.3
3+
Polyaluminium iron(III) [Al(OH)3-xClx]n Solution Tank Al 59
3+
chloride + FeCl3 1.3 Acid resistant Fe 6 – 15 1
pump 2.3 – 2.5

8 April 2004
 ATV-DVWK-A 202E

According to model calculations by the German As precipitants, Fe3+ and Al3+ behave similarly. It
Federal Environmental Office (UBA, 1997) for the is, however, to be noted that with iron the pH value
addition of heavy metal into sewage sludge with optimum for precipitation is lower by ca. one unit
which, on average, a β-value of 1.2 and an adsorp- (see 3.6.1). The iron flakes are in general heavier,
tion rate in the sewage sludge of 90 % were as- compacter and more resistant to shear than alu-
sumed, no limiting values but rather standard val- minium flakes. This is of significance with the de-
ues (Table 2) were formulated due to the marginal sign of the separation system.
increase with the inputs of heavy metal via the
path of precipitation and flocculation salts. In com- With calcium phosphate precipitation there are
parison with the positive effects (P, COD, and AOX various known possible reactions. It is, however,
reduction) the increase in metal is tolerable. not predictable which of these reactions will take
place in the wastewater. The most important pre-
Table 2: Standard values for precipitation cipitation product with the bonding of phosphate is
and flocculation agents containing hydroxyl apatite
iron or aluminium (UBA, 1997)
5Ca2+ + 3PO43- + OH- → Ca5(PO4)3OH
Standard Standard Standard
value value value As – with the exception of soft water - calcium is
[mg/kg STM] [mg/kg Fe] [mg/kg Al]
Lead (Pb) 90 260 427
always sufficiently available, the purpose is primar-
Cadmium (Cd) 1 2.9 4.7 ily not the input of calcium ions Ca2+, but much
Chrome (Cr) 90 260 427 more an increase of the pH value with precipitation
Copper (Cu) 80 230 380 treatment through the dosing of slaked lime
Nickel (Ni) 20 58 95
Ca(OH)2. Therefore, with water of high hardness, a
Mercury (Hg) 0.8 2.3 3.8
Zinc (Zn) 250 720 1190 precipitation can also be carried out following input
AOX 100 100 of another alkaline solution.

Some precipitants contain metals (e.g. barium), In particular, in connection with biological P-
which are not listed in the Klärschlammverordnung removal, a reaction of magnesium and ammonium
(German Sewage Sludge Ordinance), but which, with phosphorus can result under the formation of
with dilution of the precipitant using water, lead to magnesium-ammonium-phosphate (MAP) This
operating problems (incrustation). spontaneous MAP formation can lead to incrusta-
tion in pipelines and machine components. A de-
A regular quality control is to be ensured by manu- liberate precipitation of MAP is too cost-intensive
facturers and suppliers of the precipitants. A pro- due to the necessary high dosing of magnesium.
duction data sheet should be provided with each
delivery. In addition, a test certificate with analyses
of the delivery should be attached. 3.4.2 Competing Reactions

Simultaneously with the phosphate precipitation

3.4 Chemical Reactions reaction several competing reactions occur which,
seen technically, lead to an increased consumption
3.4.1 Precipitation Reaction of precipitants and thus lead to an increase in the
quantity of sewage sludge. Essentially the follow-
Phosphate removal using metal salts is based ing are to be differentiated:
essentially on the precipitation of the PO43- through • hydroxide formation Me3+ + 3OH- → Me(OH)3,
Me3+, i. e. through the formation of the only slightly • carbonate formation Ca2+ + CO32- → CaCO3,
soluble phosphate compounds FePO4 and AlPO4, • complexing with organic substances,
according to the reaction equation • adsorption reactions.

Me3+ + PO43- → MePO4

April 2004 9
ATV-DVWK-A 202E

The most important competing reactions with Fe3+ • the concentration of compounds which can at-
and Al3+ are precipitation using the hydroxyl ion tach to solid matter as a type of “protective
OH- and, with Ca2+, formation of carbonate. layer” sheathing and thus make the effect of
floc-promoting chemicals more difficult.
Organic substances can be removed through pre-
cipitation reactions to a minor degree only. The On the other hand, attention must be paid that
decisive mechanisms of the removal of organic other treatment objectives, in particular nitrification,
substances with chemical-physical phosphate re- are not affected negatively through the dosing of
moval are, on the other hand, the coagulation of precipitants. In particular, the reduction of pH values
organic colloids as well as the inclusion of the sus- and alkalinity is significant. In individual cases re-
pensa in flocs, whereby organic phosphorus is also medial measures have to be taken (see 3.6.1,
removed. Furthermore, with precipitation, surfaces 3.6.2, 3.6.4 and in particular ATV-DVWK-A 131E,
capable of adsorption are formed on a large scale Section 5.2.9).
so that the addition of adsorbing materials can be
significant. The required quantity of precipitant to be dosed is
estimated for practical reasons via the β-value.
This is defined as:
3.5 Type of and Requirement for
Precipitants
X Me / AM Me mmol / l
ßP,Prec = in
Considered chemically, iron and aluminium salts X P,Prec / AM P mmol / l
are very similar in their effectiveness. With practi-
cal employment, however, in part significant differ- with
ences occur which, primarily, are to be explained
by the composition of the wastewater and the thus XMe required quantity of precipitant (metal) in
related secondary reactions. A first orientation on mg Me/l wastewater
the effectiveness of precipitants is provided by XP,Prec phosphorus to be precipitated in mg P/l
laboratory tests (see for example DVGW1 Standard wastewater
W 218 „Flockentestverfahren” [Floc test proce- AMMe atomic mass of the metal in mg/mmol and
dures]). AMP atomic mass of the phosphorus in
mg/mmol
The necessary requirement for precipitant for the
maintenance of a monitoring value with precipi- The phosphorus to be precipitated XP,Prec corre-
tants containing iron and aluminium salts is influ- sponds with the phosphorus in the inflow minus the
enced by: phosphorus in the effluent of the respective stage,
reduced by the heterotrophic phosphorus and by
• the dosing point
the phosphorus bonded through a biological phos-
• the phosphate load of the wastewater taking phate removal (see calculation example, Appendix
into account the type and concentration of the A.4.1, Equation A.10).
phosphorus,
As reference value for βPrec with pre-precipitation,
• the extent of the biological phosphorus bonding,
simultaneous precipitation and post-precipitation
• the size of the monitoring value, βPrec is to be set as = 1.2. To be noted is that the
necessary β values increase with tighter monitoring
• the pH value of the raw wastewater,
values and reducing phosphate concentrations,
• the concentration of substances which, together which have to be precipitated. Accordingly, with
with the precipitants used, form complexes, e.g. flocculation filtration and post-precipitation as sec-
between iron ions and humic matter, ond stage, a βPrec of at least 2.5 is to be applied.

1
German Technical and Scientific Association for Gas and Water
(DVGW)

10 April 2004
 ATV-DVWK-A 202E

3.6 Influencing Factors on 3.6.3 Further Chemical Influencing

Precipitation Variables

3.6.1 pH Value With otherwise identical wastewater compositions

the requirement for precipitant increases with:
The solubility of the meal phosphates formed with • increasing turbidity (suspended solids and col-
the chemical-physical phosphate removal is de- loids) – due to flocculation occurring in parallel,
pendent on the pH value. The smallest solubility of • increasing content of dissolved organic matter –
FePO4 lies in the pH range 5.0 to 5.5, and that of due to competing complex formation reactions.
AlPO4 in the pH range 6.0 to 7.0. In these ranges, the
best precipitation results are, theoretically, to be ex- 3.6.4 Physical Influencing Variables
pected. The floc formulation required in addition to
the chemical-physical phosphate removal, how-
ever, possibly does not run satisfactorily in these With phosphate precipitation and flocculation the
pH ranges. following physical constraints are to be maintained:

In general therefore, an effective phosphate re- • The thorough mixing of the precipitant must be
moval is achieved in practice with pH values of 6.5 guaranteed in the shortest time so that the di-
to 8.5. Under certain circumstances an increase of rect reaction of the metal ion with the phosphate
the pH value through the input of an alkaline solu- ion is encouraged. In practical application this
tion or lime is necessary. phase, as a rule, is coupled with that of the for-
mation of micro-flocs. The detention time of the
If no precipitants containing metals are used but wastewater in the mixing zone/in the mixing re-
rather lime, it is not the quantity of lime added but actor should be ca. one minute. The energy in-
rather the pH value which is thus achieved which is put is to be so adjusted that a power density in
decisive for the success of the precipitation. the range of 100 W/m³ to 150 W/m³ is achieved.

With pre-precipitation using slaked lime and with • Although the energy density in the phase of
soft water, only a small amount of slaked lime is flocculation formation must be sufficiently high
required in order to achieve a high pH value. Heav- in order to enable the necessary collision of the
ily buffered wastewater, on the other hand, re- particle and micro-flocs it must, however, not be
quires higher quantities of slaked lime; here the so high that the flocs already formed are not
simultaneously occurring calcium carbonate pre- destroyed again. Technically this is effected
cipitation with pH values > 9 can lead to the forma- through scheduling a multi-phase floc formation
tion of crusts and thus to considerable operating (micro-floc formation, chronologically coupled
difficulties. with the precipitant mixing; macro-floc formation
which, on their part, can be conceived again us-
3.6.2 Alkalinity ing staged power density). The reaction time of
the macro-floc formation should be ca. 20 to 30
The extent of the pH modification depends on the minutes. The power density is, on average , set
quantity of the precipitant added and the buffer at ca. 5 W/m³ (for multi-stage floc formation
capacity of the wastewater, characterised by its these values are to be divided and graduated).
alkalinity Kww4,3. With soft wastewater with low al- The formation of easily separable macro-flocs
kalinity a too low a pH value can easily arise with can also be supported through the addition of
the dosing of Al and Fe salts, which, for example, polymers as flocculation aid (see ATV-DVWK-M
is a disadvantage for nitrification. 274 [Not available in English]). The possible in-
put of contaminants (polyacrylamides and di-
Then the employment of alkaline Al compounds or
thiocarbonates) is to be noted.
the combination of acid salts and slaked lime is
advantageous.

April 2004 11
ATV-DVWK-A 202E

With multi-stage flocculation the flocculation stages with the [German] Construction Regulation List A,
are operated with reducing power density in the Part 1, No. 15 or in accordance with a National
direction of flow, while the detention time in the General Technical Approval. Precipitants are haz-
sub-stage remains ca. the same size. ardous substances within the meaning of § 3 of the
[German] Law on Protection against Hazardous
Substances (Chemical Law – [in German =
3.6.5 Influence of the Biological Phase
ChemG]) and of § 4 of the [German] Ordinance on
on the Precipitant Requirement Protection against Hazardous Substances (Haz-
ardous Substance Ordinance – [in German =
In general, with nitrification/denitrification, an in-
GefStoffV]). With the handling of precipitants Sec-
creased biological phosphate removal occurs.
tion 5 of the [German] Hazardous Substance Ordi-
Through this the precipitant requirement becomes
nance “General Regulations for the Handling of
smaller (see Section 3.5). The increased biological
Hazardous Substances” is to be noted in particu-
phosphorus bonding in the form of polyphosphates
lar.
causes an increased yield of surplus sludge of ca.
3 g TS/g bonded phosphorus.
The storage containers are to be so dimensioned
that the complete load of a silo- or tank vehicle can
be accepted (> 25 m³). Attention is to be paid to a
3.7 Storage and Dosing of Precipitants
sufficient reserve corresponding with the require-
ment at weekends and holidays.
Precipitants are supplied as a solid, a solution or
as a suspension (see Table 1). Facilities for stor-
The arrangement of the dosing station and the
age and, possibly, solution and dosing are to be
dosing of the precipitant are dependent on
designed dependent on the condition at delivery
method. Appropriate explanations are given in
and on the aggressiveness, danger of forming
Section 4 with the description of the individual
lumps, flow ability and abrasion through undis-
dosing method.
solved components. Storage containers are made
from steel, concrete or plastic. With steel and con-
Control or regulation of the precipitant dosing can
crete, corrosion protection through appropriate,
be carried out dependent on time taking into ac-
approved coatings is required. With liquid precipi-
count measured hydrograph curves (small scale
tants dosing can be direct from these containers;
wastewater treatment plants), proportional to quan-
with solid precipitants additional facilities for solu-
tities of water (medium-sized wastewater treatment
tions are to be planned, with quicklime also a
plants) or proportional to phosphorus load (large
quenching facility. If required, the facilities or parts
wastewater treatment plants). In addition, a dosing
thereof are to be accommodated in buildings. Pipe-
proportional to the phosphate concentration has
lines, as a rule, are manufactured from corrosion
also proved successful.
resistant plastic.

With dosing proportional to water quantities an

Precipitants are water-hazardous substances
increased combined wastewater inflow can lead to
within the meaning of § 19g of the [German] Water
overdosing if a limitation of the dosing is not
Resources Management Law (in German = WHG)
planned.
and must meet the requirements of §§ 19g to
19I WHG. Furthermore, the water laws of the Ger-
With lime precipitation dosing must be undertaken
man Federal States apply as well as the respective
via a pH value regulation.
Ordinance for Facilities for Handling Water-
hazardous Substances and on Special Operations
Advisory Leaflet ATV-DVWK-M 206E deals in de-
(in German = VAwS).
tail with continuous measurement, with automation
concepts as well as storage and dosing technol-
Complete and prescribed dosing stations are of-
ogy.
fered by relevant specialist firms and suppliers of
precipitants. Attention is to be paid that the con-
tainers have a nationally technically approved suit-
ability certificate, i.e. either suitable in accordance

12 April 2004
 ATV-DVWK-A 202E

4 Methods (see 3.6.4). If no position with sufficient turbulence

is available (hydraulic jump, drop structure), the
efficiency can be improved considerably through
Various methods are defined depending on the increasing the power density by mixing the precipi-
point of application of the precipitant: tant thoroughly at the dosing point.

• pre-precipitation, Preferred dosing points which satisfy these condi-

• simultaneous precipitation, tions are the inverted siphon inlet to a circular pri-
• post-precipitation and
mary or secondary settlement tank with high turbu-
• flocculation filtration
lence in the inverted siphon and small turbulence
With pre-precipitation the precipitation products are in the central structure.
separated out in the primary settlement tank and
with simultaneous precipitation in the secondary In channels the thorough mixing can be improved
settlement tank. The precipitation products with through the installation of a baffle or the operation
post-precipitation and with flocculation filtration are of a submerged pump or propeller. If the wastewa-
separated using independent stages (sedimenta- ter at the dosing point contains no coarse materials
tion, flotation or filtration). Fundamentally these
which can lead to blockages, a static mixer is also
methods can also be combined (two-stage precipi-
suitable.
tation), e.g. pre-precipitation and simultaneous
precipitation or simultaneous precipitation and
The methods and their performance are drawn up
post-precipitation. In each case attention is to be
in Table 3.
paid to sufficiently thorough mixing and flocculation

Table 3: Precipitation methods – dosing points, performance, floc separation

Pre-precipitation Simultaneous Post-precipitation Flocculation

precipitation filtration
Observable monitoring 2 1 1 0.5
value *
(mg/l P)
Dosing point(s) Before primary set- Before / in / after After secondary Twofold as with simul-
tlement tanks aeration tanks, after settlement tanks taneous and post-
(e.g. venturi, aerated biological filters or precipitation
grit chamber) contactors
Thorough mixing Points of higher tur- Points of higher tur- Mixer As with simultaneous
bulence bulence and post-precipitation
Place of floc separation Primary settlement Secondary settle- Additional sedimen- 1st Stage: existing
tanks ment tanks tation or flotation secondary settle-
tanks ment tanks
2nd Stage: additional
filters

* Under favourable conditions and optimum operating conditions even lower values can be observed.

4.1 Pre-precipitation through this, the denitrification more difficult.

Slaked lime up to pH values of 9.5 is employed,
With the pre-precipitation method (Fig. 1) the pre- iron(II) salts only in combination with an aerated
cipitants are added before the primary settlement grit chamber.
tank or before the grit chamber.
With biofilters as main stage, pre-precipitation is
With this method, in addition to the phosphates, the only possibility to remove phosphates, possibly
organic and filterable substances are also re- also as two point precipitation (pre-precipitation
moved. The subsequent nitrification is made easier and flocculation filtration).

April 2004 13
ATV-DVWK-A 202E

Diagram 1: Dosing points pre-precipitation

Diagram 2: Dosing points simultaneous precipitation

4.2 Simultaneous Methods Through the addition of precipitants the inorganic

part of the solid content increases in the aeration
4.2.1 Simultaneous Precipitation tank (Section 5.1).

With simultaneous precipitation (Diagram 2) the With the biological filter method the precipitant is
addition of the precipitant takes place, as selected, dosed exclusively into the inlet to the biological
before the aeration tank, in the aeration tank, in the filter trough, with rotating biological contactors the
inlet to the secondary settlement tank or in the dosing can take place both in the inlet to the bio-
return sludge. The two dosing points: inlet aeration logical contactor trough and into the secondary
tank and return sludge, are not to be recom- settlement tank.
mended if an anaerobic tank is available for the
biological phosphate removal (Section 4.2.2). The precipitant and the resultant product remain in
the aeration tank for the duration of the sludge age
and can in this period buffer high phosphate
With the employment of trivalent iron salts the inlet peaks. The buffer capability can be ensured
to the secondary settlement tank has shown itself through a minimum base load dosing.
to be favourable as dosing point.

14 April 2004
 ATV-DVWK-A 202E

Simultaneous precipitation can also be applied moval alone, facilities for the supplementing of
with aerated and unaerated ponds. With unaerated simultaneous precipitation are to be supplied.
ponds the use of lime (avoidance of the formation
of iron sulphide) is recommended. It is, however The addition of precipitant for the supplementary
also pointed out that, with many unaerated ponds, simultaneous precipitation to the biological phos-
a significant precipitation of calcium phosphate phate removal should take place either in the inlet
occurs, at least temporarily, even without the addi- to the secondary settlement tank (trivalent precipi-
tion of precipitant, as a result of the increase in pH tants only) or into the aeration tank or in the return
with the formation of algae. sludge (see Diagram 2).

4.2.2 Simultaneous Precipitation for the 4.3 Downstream Stages

Supplementing of Biological The methods of post-precipitation and flocculation
Phosphate Removal filtration are characterised in that the precipitation
and flocculation as well as the separation of the
As the observation of the monitoring values is not flocculated substances take place in a separate
always possible through biological phosphate re- stage downstream from the biological treatment.

Diagram 3: Dosing points post-precipitation

Diagram 4: Dosing points flocculation filtration (in combination with BioP, with pre- and
simultaneous precipitation see Diagrams 1 and 2)

April 2004 15
ATV-DVWK-A 202E

4.3.1 Post-precipitation 4 mg/l Fe or 2.5 mg/l Al are added. The dosing of

polymers should be done without in order to avoid
The precipitants with post-precipitation (Diagram 3) operational problems (sticking) and because, as a
are added into the inlet to the downstream separa- rule, the effect is insignificant.
tion stage, whereby the thorough mixing in the
channel takes place using appropriate baffles The mixing processes occurring with the flow
(static or dynamic mixers) or in separate floccula- through the filter encourage the formation of flocs.
tion tanks. A flocculation area is required for the Size, shape and structure of the filter grain as well
formation of the separable flocs (see Section as the structure, loading and filtration rate of the
3.6.4). filter determine the pressure loss. The efficiency,
the required energy input into the filter for macro-
The flocs are separated by sedimentation in a set- filter formation and a practical filter service life limit
tlement tank or through lamination separators or the possible filtration rates. For vertically down-
through flotation. With sedimentary separation ward streamed open filters this allows a dimen-
methods the flocculation process can be improved sioning for the case of dry weather (QDW,h,max) with
by feeding return sludge into the flocculation stage. a filter rate of 6 m/h up to 8 m/h, whereby the plant
with rainy weather can be fed with 2 QDW,h,ma.
The post-precipitation stage forms its own process Within this range the treatment performance
unit and barely influences the upstream processes. achievable using flocculation filtration is almost
Furthermore, the variations in inflow concentra- independent of the filtration rate. Further informa-
tions are relatively small and thus a better match- tion on flocculation filtration is contained in Stan-
ing of the precipitant dosing is possible. dard ATV-A 203 [Not available in English].

4.3.2 Flocculation Filtration 4.4 Two-stage Precipitation

Flocculation filtration (Diagram 4) can be employed With two-stage precipitation two of the processes
as second stage only, for example following pre- or described in the previous sections are combined,
simultaneous precipitation or biological phosphate e.g. as simultaneous precipitation and flocculation
removal. filtration, and also pre- and simultaneous precipita-
tion or as simultaneous- and post-precipitation.
The dosing of the precipitant takes place in the This takes place for the following reasons:
inlet of the flocculation filter. According to available
experience monitoring values of 0.5 mg/l P can be • early relief of the following process stages,
maintained using flocculation filtration. Lower
monitoring values can also be maintained with • economical use of chemicals (from experience
favourable constraints. With a βPrec of ≥ 2.5 neces- the overall degree of effect with two-point pre-
sary here, the phosphate concentration in the in- cipitation is greater than with the dosing of the
flow should not be higher than ca. 1 mg/l in order total amount of precipitants at one input point),
to achieve still tolerable filter service lives. For the
ecological aspects of the employment of organic • specifically for the protection of the filter with
polymers as flocculation aid, attention is drawn to flocculation filtration.
Advisory Leaflet ATV-M 274 „Einsatz organischer
Polymere in der Abwasserreinigung“ [Employment A regulation or control of the dosing can be limited
of Organic Polymers in Wastewater Treatment (Not to the second stage.
available in English)], Section 8.

With flocculation filtration the flocculation takes

place in the filter. The adjustable energy input with
intensive mixing, above all, however, the type and
quantity of precipitant, must be matched very care-
fully to the filter. From experience not more than

16 April 2004
 ATV-DVWK-A 202E

5 Influence of Precipi- inhibition of the nitrification, for reasons of safety,

an alkalinity of 1.5 mmol/l should be maintained. In
tation/Flocculation on critical cases an alkaline precipitant should be
employed, possibly combined with slaked lime.
the Treatment of With dosing of slaked lime the pH value may not
be increased too heavily so that no return solution
Wastewater and of aluminium takes place and a calcium carbonate
Sludge precipitation is avoided (see 3.6.1).

The inorganic part of the activated sludge in-

5.1 Influence of Phosphate creases as a result of the simultaneous precipita-
Precipitation on the Biological tion. The additional surplus sludge produced must
Processes be taken into account with the dimensioning of the
activated sludge plant. With pre- and post-
The biological degradation of organic substances precipitation also one can reckon with the same
and the biochemical oxidation and reduction of order of this chemical sludge production.
nitrogen are influenced
• with pre-precipitation (see 4.1): through in-
crease of the N/BOD5 ratio and modification of 5.2 Influence of Phosphate
the alkalinity of the wastewater as well as Precipitation on the Sludge
through raising the sludge age,
5.2.1 Solid Matter Load
• with simultaneous precipitation (see 4.2): as a
rule, through improvement of the settling and Through the transfer of dissolved and suspended
thickening characteristics as well as the in- substances in settleable flocs the share of solid
crease of the inorganic part of the activated matter is increased. The additional solid matter
sludge, through increased yield of surplus load results from the quantity of the precipitant
(waste) sludge and a lowering of the sludge added, from the compounds formed as well as
age, abatement of the alkalinity and, depending from the quantity of solid matter removed.
on the type of precipitant, the stimulating or in-
hibiting effect on the nitrification, In practice the phosphates, hydroxides and other
• with post-precipitation (see 4.3.1): no or only substances also precipitated formed from the pre-
insignificant influencing with the return feed of cipitants give a dry solid matter content of:
sludge from the post-precipitation stage into the • 2.5 g/g, referred to iron, and
plant inlet.
• 4 g/g, referred to aluminium.
With all methods of precipitation it is important that
a subsequent biological stage remains supplied The overall increase in solid matter can be calcu-
with sufficient phosphorus (0.7 mg/l P to 1 mg/l P lated from the above specific values and the dosed
per 100 mg/l BOD5). active substance (see calculation example in the
Appendix). With increased biological P-removal
The change of the N/BOD5 ratio as a result of pre- one must reckon with an increase of the solid mat-
precipitation, through the abatement of the BOD5- ter load of ca. 3 g/g referred to phosphorus re-
loading of the biological stage, has positive effects moved.
on the nitrification, however, usually negative re-
sults for the denitrification. With the addition of slaked lime as precipitant on
has to reckon with an increase of solid matter of
The specific reduction of the alkalinity is referred ca. 1.35 times the dosed quantity. The specific
normally to a kilogramme of metal ions, although it growth of solid matter is, with:
is really dependent on the content of the acid resi- • pH values of about 9.5 up to ca. 50 g/(I . d),
dues in the precipitant. It is 54 mol/kg with iron and
111 mol/kg with aluminium. In order to avoid an • pH values of about 11 up to 200 g/(I . d).

April 2004 17
ATV-DVWK-A 202E

5.2.2 Sludge Volumes of precipitants. In the case of an originally lower

solid matter content of the secondary sludge with
The additional sludge volumes produced with simultaneous precipitation a slight increase with
phosphate removal result from the solid matter increasing dosing occurs. Through this the forma-
load and the water content or solid matter content. tion of bulking sludge can also be combated. With
If a higher solid matter content is achieved, despite post-precipitation the share of water-rich hydroxide
increased solid matter yield from the precipita- flocs increases with increasing dosing. Through
tion/flocculation reaction, smaller sludge volumes this the solid matter content in the tertiary sludge is
of activated sludge are possible. abated.

The selected method of operation (pre-, simulta- If metal salts (β>2) are also employed for the for-
neous or post-precipitation) and type and quantity mation of the macro-flocs (see Section 3.2), the
of precipitant employed have a significant influence solid matter content is reduced as a result of hy-
on the solid matter content of the flocs formed. droxide floc formation. These can be countered
through addition of organic flocculants (polyelectro-
With pre-precipitation the solid matter content of lytes) in place of additional metal salts (see ATV-
the primary sludge increases with increasing input M 274).

18 April 2004
 ATV-DVWK-A 202E

Appendix A • XP,Prec phosphorus (mg/l)eliminated through

precipitation, to be calculated
Calculation Examples • βPQ of the relative quantity of precipitant to be
selected (mol Me/mol XP,Prec)
as
A.1 Basic Elements of Calculation
Q DW,d
B d,PQ = X P,Prec ⋅ β Prec ⋅ (g/d precipitant)
With the following calculations of precipitant re- z
quirements and yield of solid matter the relative (A.2)
atomic masses (AMX) of the elements phosphorus
(AMP = 31.0 g/mol P), iron (AMFe = 55.8 g/mol Fe) To cover the peaks of the phosphorus content in
and aluminium (AMAl = 27.0 g/mol Al) are em- the inflow – similarly as with nitrogen (ATV-DVWK-
ployed. The data sheet belonging to each precipi- A 131E, fN in Table 8) – a peak factor fP dependent
tant contains details of the content of active sub- on the size of the plant and the sludge age (peak
stance in delivery form (ASMe) in one of the follow- load adjustment as a result of tank volume) is ap-
ing forms (see also Table 1): plied, which is involved for the design of the dosing
facility(ies). With pre-precipitation the greatest
▪ kg Me per kg precipitant = ASMe value from Table 8, ATV-DVWK-A 131E, is rec-
(Definition used here) ommended; with post-precipitation, as a result of
▪ % Me (mass percent- = 100 ⋅ ASMe the previous peak load adjustment, the smallest.
age) With this the maximum hourly dosing is:
▪ g Me per kg precipitant = 1000 ⋅ ASMe
fP ⋅ QDW, d
▪ mol Me per2+kg precipi- = 1000 ⋅ ASMe/AMFe Bh,PQ = XP,Prec ⋅ βPrec ⋅ (g/h precipitant) (A.3)
3+
tant for Fe and Fe : 24 ⋅ z
= 1000 ⋅ ASMe/55.8
= 17.9 ⋅ ASMe In general the precipitant is dosed as a solution. If
3+ the precipitant solution is delivered by the manu-
▪ for Al : = 1000 ⋅ ASMe/AMAl
facturer with a density of ρPS, then the volume flow
= 1000 ⋅ ASMe/27.0
to be dosed is QPQ of the dissolved precipitant:
= 37.0 ⋅ ASMe
B d,PQ B h,PQ
▪ Density of the precipitant solution ρPS (kg/m3 solution) Q d,PQ = (l/d) or Qh,PQ = (l/h) (A.4)
ρPS ρPS

From the respectively specified data the active A powder or granulate formed precipitant is applied
substance content ASMe (kg/kg) of a precipitant on site and leads to a solution with a precipitant
used in an example can be calculated using the concentration of cPS (kg/m3 precipitant); a dry dos-
above equations. ing is often also possible. The solution applied lies
in the area of 10 % precipitant content and the
From the details for the content of iron WSFe and solution density cPS (100 kg/m3) which results can
aluminium WSAl an interaction coefficient z is cal- be monitored using a hydrometer. The volume
culated with the aid of the relative atomic masses flows of precipitant solution are the:
(AMX):
B d,PQ B h,PQ (l/h) (A.5)
Q d,PQ = (l/d) or Q h,PQ =
c PS cPS
AMP AMP
z= ⋅ AS Fe + ⋅ AS Al = 0.555 ⋅ AS Fe + 1.148 ⋅ AS Al (A.1)
AMFe AM Al The delivery of the pump(s) is to be designed at
max. QPQ.
The average quantity of precipitant to be dosed
Bd,PQ (g/d precipitant) then results as: The on average solid matter yielded (chemical
waste sludge) WSd,Chem (g/d DR) from precipitation
• QDW,d the daily wastewater quantity with dry and flocculation are calculated in accordance with
weather (m3/d) the statement in Section 4.2.1 on the basis of the
dosed quantity of iron or aluminium. Basis for this
with powder or granulate-formed precipitants, the

April 2004 19
ATV-DVWK-A 202E

calculated mean precipitant quantity Bd,PQ in ac- CP = 1.5 mg/l P

cordance with Equation A.2 and the content of Monitoring value: CP = 2.0 mg/l P
active substance of the precipitant ASMe:
1.1 and nitrification
WSd,Chem = Bd,PQ ⋅ (2.4 ⋅ ASFe + 4.0 ⋅ ASAl ) (g/d TS) (A.6)
1.2 and denitrification
1.3 and biological P-removal

If the precipitant is delivered from the manufacturer

2. Activated sludge process with simultaneous
as solution and is then dosed, the mean solid mat-
precipitation
ter WSd,Chem (g/d TS) produced is determined
Selected mean operating value:
through the combination of Equations A.5 and A.6
CP = 1.0 mg/l P
as:
plus flocculation filtration
Selected mean operating value:
CP = 0.2 mg/l P
WS d,Chem = B d,PQ ⋅ (2.4 ⋅ AS Fe + 4.0 ⋅ AS Al ) (g/d TS) with a monitoring value of : CP = 0,3 mg/l P
(A.7a)
2.1 and nitrification
or 2.2 and denitrification
2.3 and biological P-removal
WS d,Chem = Q d,PQ ⋅ c PS ⋅ (2.4 ⋅ AS Fe + 4.0 ⋅ AS Al )

(g/d TS) A.3 Load and Dimensioning Assumptions

(A.7b)

With the treatment process using denitrification Plant capacity: PT = 15,000 I

and biological phosphorus removal, in addition to
the chemical surplus sludge, also addition solid
matter is produced as a result of biological phos- Specific wastewater yield Www,d = 180 l/(I⋅d)
phorus compounds. These (WSd,BioP in g/d TS) are
Dry weather flow QDW,d = 2,700 m3/d
calculated in accordance with ATV-DVWK-A 131E,
Section 5.2.4 as follows: Specific wastewater load BOD5 Bd,BOD = 60 g/(I⋅d)

After primary settlement (in the Bd,BOD = 40 g/( I⋅d)

WS d,BioP = 3.0 ⋅ QDW, d ⋅ XP,BioP (g/d TS) (A.8)
example)
Specific wastewater load Ptot Bd,P = 1.8 g/( I⋅d)
A.2 Treatment Methods Investigated and
Monitoring Values Ptot After primary settlement (in the Bd,P = 1.6 g/( I⋅d)
example)
Below are the wastewater treatment methods in-
vestigated together with the monitoring values Phosphorus bonding in the activated sludge:
applied. The mean operating values used as basis
for the calculation are given respectively in brack- The bonding of phosphorus in the activated sludge
ets. For flocculation filtration a lower mean operat- (biomass) XP is calculated as share [PB (-, %)] of
ing value of the upstream activated sludge process the BOD5 CBOD,InBio fed in. Bonding takes place via
of 1.0 mg/l is required. the biological cell build up in the activated sludge
with nitrification (PBBM) and via the increased P-
Treatment method investigated Bonding, which is dependent on the denitrification
1. Activated sludge process with simultaneous (PBDeni) and a possibly existing anaerobic primary
precipitation settlement tank:
Selected mean operating value:

20 April 2004
 ATV-DVWK-A 202E

Cell build-up only with this an interactive coefficient results:

XP,BM = PBBM ⋅ CBOD,InB (A.9a) z = 0.555 ⋅ ASFe + 1.148 ⋅ ASAl

= 0.555 ⋅ 0.010 + 1.148 ⋅ 0.082 = 0.0056 +
0.0941 = 0.0997
With denitrification
From this granulate a solution with
XP,BioP = PBDeni ⋅ CBOD,InB (A.9b) ρPS = 100 kg/m3 is produced and dosed.

2. Iron(III) chloride (FeCl3) liquid,

With anaerobic tank
with 13.8 % Fe3+ and a density of 1.430 kg/m3
with this an interaction coefficient results:
XP,BioP = (PBDeni + PBAna) ⋅ CBOD,InB (A.9c)
z = 0.555 ⋅ ASFe = 0.555 ⋅ 0.138 = 0.0766

Types of bonding: Selected peak factors:

Simultaneous precipitation fP = 2.0
1. Nitrification (cell build-up) of the PBBM = 1.0 % Flocculation filtration fP = 1.5
CBOD,InB fed in

2. Denitrification PBDeni = 0.5 % A.4 Calculations

additional biological
P-bonding of the CBOD,InB fed in A.4.1 Calculation of the Phosphorus to
3. Additional biological PBAna = 1.0 % be Precipitated
P-removal
with anaerobic primary settle- The phosphorus to be precipitated XP,Prec (mg/l)
ment tank results from the following phosphorus balance (C
additional biological for phosphorus in the homogenised sample; X for
P-bonding of the CBOD,InB fed in filterable phosphorus; in each case mg/l P):
XP,Prec = CP,InB - CP,aM,ESST - XP,BM - XP,BioP(mg/l) (A.10)
Selected relative precipitant quantities βPrec: with

With simultaneous precipitation XP,Prec (mg/l) Concentration of the phospho-

rus to be precipitated,
With mean operating value CP = 1.5 mg/l P CP,InB (mg/l) Concentration of the phospho-
rus in the homogenised sample
βPrec = 1.2
in the inflow to the activated
With mean operating value CP = 1.0 mg/l P sludge plant (after primary
settlement),
βPrec = 1.5
CP,aM,ESSS (mg/l) Concentration of the phospho-
With flocculation filtration βPrec = 2.5 rus in the homogenised sample
in the effluent of the secondary
Selected precipitant: settlement tank, annual mean
value (mean operating value),
1. Aluminium-Iron(III) Sulphate as granulate
XP,BM (mg/l) Phosphorus required for cell
[Al2(SO4)3 + Fe2(SO4)3] ⋅ n H2O build-up with carbon removal
and nitrification,
with 1.0 % Fe3+ and 8.2 % Al3+ XP,BioP (mg/l) Phosphorus removed through
i.e. WSFe = 0.010 kg Fe/kg granulate and biological P-removal (denitrifi-
ASAl = 0.082 kg Al/kg granulate cation and anaerobic primary
settlement tank).

April 2004 21
ATV-DVWK-A 202E

In the above sections assumptions are made and while with denitrification and anaerobic primary
calculation information is given with regard to tank (additional 1.5 %)
these values (CP,aM,ESST). The calculation of XP,Prec
XP,BioP = (PBBM + PBAna) ⋅ CBOD,InB
for the six methods investigated took place with the
= (0.005 + 0.01) ⋅ 222
aid of Equations A.9 and A.10. The calculation
= 3.3 mg/l P
process and the results are summarised in Table
A.1. The table also contains the β-values and the
relevant product XP,Prec ⋅ βPrec required for the Were additionally bonded (Appendix A.2: Process
calculation of the precipitant quantity. The calcula- 1.3 and 2.3).
tion process is explained using the treatment
process 1.2 (activated sludge process with nitrifica- From these phosphorus concentrations XP,Prec is
tion and denitrification): calculated in accordance with Equation A.10 (Col-
umn 6). The product in Column 8 is formed from
The content of total phosphorus CP,InB and of the selected βPrec (Column 7; see also Section A 3)
CBOD,InB in the inflow to the activated sludge tank and XP,Prec.
with all treatment processes investigated was:
CP,InBio = 1000 ⋅ (1.6/180) = 8.9 mg/l P
(Column 2, Table A.1) A.4.2 Calculation of the Precipitant
Quantities
CBOD,InB = 1000 ⋅ (40/180) = 222 mg/l

The annual mean value for total phosphorus in the The necessary precipitant quantities for both the
effluent of the secondary settlement tank is se- selected products are determined with the aid of
lected as: Equations A.2 to A.5. The necessary parameters
CP,aM,ESST = 1.5 mg/l P (Column 3). for this (XP,Prec ⋅ βPrec; QDW,d; z; fP; ρPS; cPS) are
given or calculated in the previous sections. The
The phosphorus required for cell build-up in Col- results are summarised in Table A.2 for the proc-
umn 4 with 1 % of the inflow BOD5 (CBOD,InB) is: esses investigated. With processes using floccula-
tion filtration, in addition to the individual steps of
XP,BM = PBBM ⋅ CBOD,InB = 0.01 ⋅ 222 = 2.2 mg/l P. the two-stage precipitation, the precipitant demand
of the total process is given at the foot of the table.
For process 2.2 in Appendix A.2 (denitrification)
0.5 % of CBOD,InB is biologically bonded (Column 5):
XP,BioP = PBDeni ⋅ CBOD,InBo = 0.005 ⋅ 222 = 1.1 mg/l P

22 April 2004
 ATV-DVWK-A 202E

Table A.1: Calculation of the phosphorus content to be precipitated XP,Prec and β-values

Process + CP,InB - CPaM,ESST - XP,BM - XP,BioP = XP,Prec βPrec XP,Prec ⋅ βPrec

Unit: mg/l mg/l mg/l mg/l mg/l - mg/l
Column: 2 3 4 5 6 7 8
Activated sludge process (Compare Appendix A.2 “Treatment processes investigated”
1.1 8.9 1.5 2.2 0.0 5.2 1.2 6.24
1.2 8.9 1.5 2.2 1.1 4.1 1.2 4.92
1.3 8.9 1.5 2.2 3.3 1.9 1.2 2.28
2.1 8.9 1.0 2.2 0.0 5.7 1.5 8.55
2.2 8.9 1.0 2.2 1.1 4.6 1.5 6.90
2.3 8.9 1.0 2.2 3.3 2.4 1.5 3.60
Flocculation filtration – downstream of the activated sludge process in Group 2
2 1.0 0.2 0.0 0.0 0.8 2.5 2.00

Table A.2: Calculated precipitant quantities (PQ) for average and peak demand

Process Aluminium-Iron(III) sulphate Iron(III) chloride solution

Average PQ Peak demand Average PQ Peak demand
Bd,PQ Qd,PQ Bh,PQ Qh,PQ Bd,PQ Qd,PQ Bh,PQ Qh,PQ
kg/d l/d kg/h l/h kg/d l/d kg/h l/h
Column 2 3 4 5 6 7 8 9
Activated sludge process (compare Appendix A.2 “Treatment processes investigated”)
1.1 169 1.690 14.1 140.8 220 154 18.3 12.8
1.2 133 1.332 11.1 111.0 173 121 14.5 10.1
1.3 62 617 5.1 51.5 80 56 6.7 4.7
2.1 232 2.315 19.3 193.0 301 211 25.1 17.6
2.2 187 1.869 15.6 155.7 243 170 20.3 14.2
2.3 97 975 8.1 81.2 127 89 10.6 7.4
Flocculation filtration – downstream of the activated sludge process in Group 2
2 54 542 3.4 33.9 70 49 4.4 3.1
Total requirement for aeration with flocculation filtration
2.1 286 2.857 22.7 226.8 372 260 29.5 20.6
2.2 241 2.410 19.0 189.6 314 219 24.7 17.3
2.3 152 1.517 11.5 115.1 197 138 15.0 10.5

April 2004 23
ATV-DVWK-A 202E

A 4.3 Calculation of the Increased Yield processes investigated are summarised in Table
of Solid Matter A.3. With the processes with flocculation filtration,
in addition to the individual steps of two-stage pre-
The increased yield of solid matter as a result of cipitation the sludge yield of the complete process
precipitation and flocculation (WSd,Chem) is deter- is given at the foot of the table
mined through the application of the active sub-
stances ASx (see Section A.3 “Selected precipi- The additional sludge yielded with processes with
tant”) and the calculated precipitant quantities Bd,PQ denitrification and anaerobic primary tank WSd,BioP
(kg/d) in Table A.2, Columns 2 and 6, in Equation is calculated using equation A.8 as well as the
A.6 (granulate or powder formed precipitant) or A.7 XP,Prec values from calculated from Table A.1 and
(precipitant solutions). The employment of Bd,PQ in are also listed in Table A.3. In addition the total
kg/d also gives WSd,Chem in kg/d. The results for the sludge quantities are determined.

Table A.3: Sludge quantities yielded

Aluminium-Iron(III) sulphate Iron(III) chloride solution

Process WSd,Chem WSd,BioP WSd,P (total) WSd,Chem WSd,BioP WSd,P
(total)
kg/d kg/d kg/d kg/d kg/d kg/d
Column 2 3 4 5 6 7
Activated sludge process (compare “Treatment processes investigated”)
1.1 72.8 0.0 72.8 59.5 0.0 59.5
1.2 57.4 8.9 66.3 46.9 8.9 55.8
1.3 26.6 26.7 53.3 21.7 26.7 48.5
2.1 99.8 0.0 99.8 81.5 0.0 81.5
2.2 80.6 8.9 89.5 65.8 8.9 74.7
2.3 42.0 26.7 68.8 34.3 26.7 61.0
Flocculation filtration – downstream of the activated sludge process in Group 2
2 23.3 0.0 23.3 19.1 0.0 19.1
Total requirement for aeration with flocculation filtration
2.1 123.2 0.0 123.2 100.6 0.0 100.6
2.2 103.9 8.9 112.8 84.8 8.9 93.8
2.3 65.4 26.7 92.1 53.4 26.7 80.1

24 April 2004
 ATV-DVWK-A 202E

Laws, Standard Specifi- • ATV-M 274 (November 1999): Einsatz or-

ganischer Polymere in der Abwasserreinigung
cations and Directives [Employment of Organic Polymers in Wastewa-
ter Treatment]
• RL 86/278 EEC Sewage Sludge Directive, Di-
• ATV-DVWK-A 400 (July 2000): Grundsätze für
rective of the Council 86/278/EEC on the pro-
die Erarbeitung des ATV-DVWK-Regelwerk
tection of the environment and in particular the
[Principles for the Preparation of ATV-DVWK
soil with the employment of sewage sludge in
Standards]
agriculture dated 12 June 1986. [In Germany
ABl. EC dated 04 July 1986 No. L 181 p. 6] • EN 1189 (December 1996): Water quality –
Determination of phosphorus by the ammonium
• Klärschlammverordnung (AbfKlärV) vom 15.
molybdate spectrometric method
April 1992, BGBl. I Nr. 21 vom 28. 04. 1992 S.
912; zuletzt geändert durch Art. 2 der Verord- • EN 12255, Part 13 (April 2003): Wastewater
nung zur Änderung abfallrechtlicher Nachweis- treatment plants – Part 13: Chemical treatment;
bestimmungen [German Sewage Sludge Ordi- Wastewater treatment through precipita-
nance dated 15 April 1992. Last amended by tion/flocculation
Art. 2 of the Ordinance on the Amendment of
• DVGW Standard W 218 (November 1998): Flo-
Verification Regulations under Water Law] dat-
ckung in der Wasseraufbereitung; Teil 2: Flo-
ed 25 April 2002, BGBl. I No. 28 dated
ckungstestverfahren [Flocculation in Water Pro-
30.04.2002, p. 1488
cessing; Part 2: Flocculation Test Process];
• Chemikaliengesetz (ChemG): Gesetz zum DVGW Bonn
Schutz vor gefährlichen Stoffen. Neugefasst
durch Bek. v. 20.06.2002, BGBl. I, S. 2090;
zuletzt geändert durch Art. 183 Verordnung Literature
[German Chemical Law: Law on the Protection
from hazardous Substances. New edition by
• Umweltverträglichkeit von Chemikalien zur Ab-
Bek. Dated 20.06.2002. Last amended by Art.
wasserbehandlung [Environmental compatibility
183 dated 25.11.2003], BGBl. I p. 2304
of chemicals for wastewater treatment], UBA-
• Wasserhaushaltsgesetz (WHG), Gesetz zur Text 39/97, Berlin: Umweltbundesamt, 1997.
Ordnung des Wasserhaushalts [German Water ISSN 0722-186 X, 1997
Resources Management Law (WHG), Law on
• Gefahrstoffverordnung (GefStoffV): Verordnung
the Ordering of water Resources dated 19. 08.
zum Schutz vor gefährlichen Stoffen. Neuge-
2002], BGBl. I Nr. 59 dated 23.08 2002, p. 3246
fasst durch Bek. vom 15.11.1999; zuletzt geän-
• ATV-DVWK-A 131E (May 2000): Dimensioning dert durch Art. 2 V v. 25.02.2004, BGBl. I, S.
of Single-Stage Activated Sludge Plants 328 [Hazardous Substance Ordinance: Ordi-
nance for the Protection from Hazardous Sub-
• ATV-DVWK-A 198E (April 2003): Standardisa-
stances. New edition published 15.11.1999;
tion and Derivation of Dimensioning values for
later amended by Art. 2 V dated 25.02.2004]
Wastewater Facilities
• ATV-A 203E (April 1995): Wastewater Filtration
Using Space Filters following Biological Treat- Reference sources
ment]
ATV-DVWK Publications:
• ATV-DVWK-M 206 (November 2001): Automa-
Deutsche Vereinigung für Wasserwirtschaft, Ab-
tisierung der chemischen Phosphatelimination
wasser und Abfall e.V., D-53773 Hennef
[Automation of Chemical Phosphate Removal]
DIN Standard Specifications:
Beuth-Verlag GmbH, D-10772 Berlin

April 2004 25