Beruflich Dokumente
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Advisory Leaflet
ATV-DVWK-M 206E
Automation of chemical phosphate removal
November 2001
ISBN 3-937758-63-1
Publisher/marketing:
GFA the publishing company of the 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@gfa-verlag.de y Internet: www.gfa-verlag.de
ATV-DVWK-M 206E
The main fields of activity of the ATV-DVWK are technical-scientific subjects and the economic as well as the
legal concerns of environmental protection. The politically and economically independent association works
nationally and internationally in the fields of pollution control, wastewater, water-hazardous substances,
waste, hydraulic engineering, hydraulic power, hydrology, soil protection and contaminated sites. The ca.
16,000 members are active in municipalities, engineer offices, authorities, firms and associations and also in
universities. Of these there are 10,000 specialists with personal membership; these are engineers, scientists,
lawyers, business persons, operating personnel and technicians. Via the corporate membership in the ATVDVWK there is access to ca. 160,000 specialists.
All rights, in particular those of translation into other languages, are reserved. No part of this Advisory Leaflet may
be reproduced in any form by photocopy, microfilm or any other process or transferred into a language usable
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Publisher:
Marketing:
DCM, Meckenheim
2 November 2001
ATV-DVWK-M 206E
Foreword
Since the publication of Advisory Leaflet ATV-M 206 Automation of the Chemical Removal of Phosphate in
July 1994 a continuous technical further development has taken place in this field. As a result of the increasing expansion of process analysis technology in wastewater treatment plants, the further development of
regulation and control strategies as well as new knowledge on the combination of a deliberate biological with
a chemical removal of phosphorus a revision and amendment of the 1994 edition has become necessary.
Authors
The original German Advisory Leaflet ATV-DVWK-M 206 was elaborated by the ATV-DVWK Specialist
Committee KA-13 Automation of wastewater treatment plants. The following have collaborated in the
preparation:
Dr. rer. nat. J.-U. Arnold, Bergisch-Gladbach
Dr.-Ing. P. Baumann, Stuttgart
Dipl.-Ing. U. Blhm, Berlin
Dr.-Ing. P. Hartwig, Hannover
Dr.-Ing. U. Jumar, Magdeburg
Dipl.-Ing. E. Michel, Waldbronn
Dr.-Ing. J. Reichert, Viersen
Dr.-Ing. S. Schlegel, Essen (Chairman)
Dr.-Ing. H.-H. Schneider, Berlin
Dipl.-Phys. Ing. W. Worringen, Dsseldorf
November 2001
ATV-DVWK-M 206E
Contents
Foreword ........................................................................................................................................................3
Authors ..........................................................................................................................................................3
User Notes......................................................................................................................................................5
1
Abbreviations .................................................................................................................................5
Introduction ....................................................................................................................................5
5.1
5.2
5.2.1
5.2.2
5.3
5.4
General.............................................................................................................................................7
Measurement of Orthophosphate (SPO4)..........................................................................................7
Molybdenum Blue Process ..............................................................................................................7
Vanadate Molybdate Process ..........................................................................................................8
Measurement of Total Phosphorus (CP) ..........................................................................................8
Operation and Maintenance.............................................................................................................8
6.1
6.2
6.3
6.3.1
6.3.2
6.3.3
6.3.4
6.3.5
6.3.6
Preamble ..........................................................................................................................................8
Measuring Sites and Dosing Points .................................................................................................8
Control and Regulation Concept for Phosphate Removal ...............................................................10
Control according to Timeplan .........................................................................................................10
Control according to P-Load ............................................................................................................11
Control according to Wastewater Flow ............................................................................................11
Regulation of SPO4 ............................................................................................................................12
Other Control Concepts....................................................................................................................14
Substitutional Value Strategies ........................................................................................................14
7.1
7.2
7.3
7.3.1
7.3.2
7.3.3
7.4
7.5
General.............................................................................................................................................15
Dosing Facilities ...............................................................................................................................16
Storage and Dosing..........................................................................................................................17
Liquid Precipitants ............................................................................................................................17
Non-Pourable Precipitants ...............................................................................................................18
Pourable Precipitants .......................................................................................................................19
Measurement of the Precipitation Concentration.............................................................................21
P-Removal by Raising the pH-Value................................................................................................21
4 November 2001
ATV-DVWK-M 206E
User Notes
This Advisory Leaflet 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 ATVDVWK-A 400). 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 Advisory Leaflet is open to
everyone. However, an obligation for application
can arise from legal or administrative regulations, a
contract or other legal reason.
This Advisory Leaflet 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 Advisory
leaflet.
Area of Application
2
AbwV
XSS
SPO4,des
CP,MV
CP,Part
CP
CCOD,InB
I
PT
F
Abbreviations
Abwasserverordnung [German Wastewater Ordinance
Concentration of suspended solids
(0.45 m)
PO4-P design value at the dosing point
e.g. in mg/l
Monitoring value for the Ptot concentration
in the effluent e.g. in mg/l
P-concentration in the effluent of the plant
due to residual suspensions e.g. in mg/l
Measured concentration of phosphorus,
e.g. in mg/l
COD in the inflow to the biological reactor
Inhabitant
Total number of inhabitants and population equivalents
Safety factor as empirical value, e.g. in
mg/l
f
FM
k
mMe
Safety factor
Precipitant
Proportionality factor
Effective metal content of a precipitant
solution, e.g. in mol/l
mP,SS
Phosphorus content of the suspended
solids, e.g. in mg/kg
SPO4
Orthophosphate-P
Q
Wastewater flow at the point of the Pconcentration measurement, e.g. in m3/h
QPF
Precipitant flow, e.g. in m3/h
UV
Ultraviolet
VAwS
Verordnung ber Anlagen zum Umgang
mit wassergefhrdenden Stoffen und ber
Fachbetriebe [German Ordinance on
plants for the handling of water-hazardous
substances and on technical operations]
WGK
Wassergefhrdungsklasse [German Water Hazard Class]
WHG
Wasserhaushaltsgesetz [German Water
Resources Management Law]
-value Ratio of mol metal to mol phosphorus related to the P-content in the influent to the
precipitation reactor.
In order to be able to assess the effectiveness of the precipitation the -value
must actually be related to the P-content
at the dosing point. In these cases higher
values result than this normal operational
definition.
Introduction
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ATV-DVWK-M 206E
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ATV-DVWK-M 206E
thoroughly practically for the relief of the biological
stage. In any case attention is to be paid that for
the subsequent biological process still sufficient
phosphorus remains in the wastewater.
Simultaneous precipitation is currently the most
widely employed process with which the addition of
precipitant takes place directly into the activated
sludge stage; the separation of the flocs takes
place in the secondary settling tank. In addition to a
good utilisation of the precipitant an improvement of
the sludge index often presents itself as a positive
side effect of simultaneous precipitation. The low Pconcentrations normal today in the wastewater
usually allow the maintenance of the monitoring
values of 2 mg/l and 1 mg/l respectively using this
simple to operate method with sufficient efficiency
of the secondary settling stage.
If, with regard to an especially weak performance
receiving water an even lower P-concentration is
required usually additional measures have to be
taken. Such measures are:
quire a certain maintenance expense and the employment of chemicals. As comprehensive information for the employment and operation of process
analysis equipment including the systems for the
pre-treatment of samples are contained in ATVDVWK Advisory Leaflet M 269 [Not available in
English], the essential analysis processes for the
determination of phosphorus compounds are only
gone into briefly in the following sections.
Using process analysis equipment both orthophosphate (SPO4) and also Ptot (CP) can be determined.
With measuring equipment for the determination of
Ptot at most a coarse filtration may be placed upstream for the protection of the equipment, as an
extensive separation of suspended solids which
contain phosphorus leads to considerably reduced
findings.
The determination of the precipitable orthophosphate compounds, on the other hand, takes place
as a rule following a sample pre-treatment, in order
to be able to analyse reliably the then extensively
solid matter-free wastewater. The sample pretreatment systems which come into question are
described in detail in ATV-DVWK-M 269.
5.2
5.2.1
5.1
General
Measurement of Orthophosphate
(SPO4)
With the molybdenum blue process (EN 1189) orthophosphate with ammonium molybdate in an acid
medium converts into complex phosphorus molybic
acid. This is subsequently converted using reduction agent into phosphorus molybdenum blue. The
light attenuation brought about by the colouring is
determined photometrically and is a measure for
the orthophosphate concentration. The process
covers the range from 0.01 to 5 mg/l SPO4 and is
therefore particularly suitable for precise measurement with low concentrations. With higher concentrations the process has to be appropriately adjusted (e.g. through dilution of the wastewater sample). The chemicals used are, however, relatively
expensive and are of only limited use.
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ATV-DVWK-M 206E
5.2.2
With the vanadate molybdate process (yellow process), orthophosphates react in the acid medium with
ammonium molybdate and ammonium vanadate into
yellow ammonium phosphorus vanado-molybdate.
The light attenuation brought about by the colouring
is determined photometrically and is a measure for
the orthophosphate concentration. Yellow wastewater
content substances influence the measured value.
This effect, as a rule, can be compensated through
special automatic calibration procedures. The process
covers a range from 0.1 to 20 mg/l SPO4. In comparison to the molybdenum blue process the chemicals
are inexpensive and last longer.
5.3
5.4
November 2001
eral equipment requirements, for measures of quality assurance, for maintenance and servicing as
well as the necessary training measures are to be
found in Advisory Leaflet ATV-DVWK-M 269.
Automation Concept
involving Metal Salts
and Sodium Aluminates
6.1
Preamble
6.2
ATV-DVWK-M 206E
Fig. 1:
November 2001
ATV-DVWK-M 206E
The dosing into the effluent of the aeration tank (F)
with a measurement in the effluent of the secondary settling stage (H), due to the long retention
time of the wastewater in the secondary settling
tank leads to large dead times. Therefore a rapid
reaction of changes of the P-load, which occurs
particularly with combined wastewater influents, is
impossible.
With a post-precipitation the precipitant dosing
takes place before the downstream stage (H). For
Table 1:
regulation measurement is carried out in the effluent of this stage (I), with control in (H). The flocculation filtration with both concepts can be realised.
In addition to the measuring site the measurement
parameter for the control and regulation tasks is of
particular significance. As an example Table 1
shows an overview of possible combinations of
measurement sites and measurement parameters
with the mainly applied simultaneous precipitation.
CP
SPO4
Measurement site
Influent biological reacPossible
The incorporation of P in the surplus sludge is to be
tor
taken into account by estimation. A continuous sampling must take place so that the sample is not influenced by a pre-treatment which, possibly, can lead
to a separation of particularly bonded phosphorus.
This can, however, be guaranteed with difficulty at
this measurement site.
Effluent biological reacImpractical
The phosphate bonded in the sludge flocs but which
tor
is not precipitable is also recorded therefore is not
suitable for inclusion in the regulation of the precipitation.
Effluent secondary
settling stage
Possible
At this measurement site only 60-75 % of the
phosphorus compounds are already available as
orthophosphate. The phosphate component which
can be removed chemically has to be estimated.
In this case the incorporation of P in the surplus
sludge is also to be taken into account.
Preparation of the sample at this measurement
site can be expensive.
Practical
Direct recording of the precipitable P-component,
through short delay times suitable for inclusion in
the regulation (with suitable dosing site).
Disadvantage: no complete recording of the monitoring parameters.
Impractical
As for the effluent of the biological reactor but,
due to long delay time not suitable for inclusion in
the regulation.
Although an input (proportional regulation) of the precipitant depending on the phosphorus concentration in the effluent of the secondary settling stage
(both SPO4 as well as CP) is not to be recommended, such a measurement can, however, provide information on the effectiveness of the precipitant input and, under certain circumstances, enables an iterative adjustment of the precipitant input. Taking into account the real wastewater flow the regulation of the Ptot concentration in the effluent of the wastewater treatment plant in combination with a subordinate regulation of the PO4-P concentration in
the effluent of the biological reactor (cascade regulation within the sense of control engineering) can increase the certainty of maintaining the monitoring values.
6.3
10
November 2001
ATV-DVWK-M 206E
Fig. 2:
QPF = k . Q . CP (Eqn. 1)
with:
QPF
k
Q
CP
=
=
=
=
=
=
safety factor
-value, e.g. 1.1 mol Fe/mol P
specific weight of the precipitant
solution, e.g. 1200 kg/m3
= effective metal content, e.g. 87 kg
mMe
Fe/1000 kg precipitant solution
55.8/30.9 = ratio of the mol masses of iron and
phosphorus
The safety factor f is to be set according to operating experience and normally lies between 1.0 and
1.5.
This concept can be realised with simultaneous
precipitation basically in two process engineering
variants (comp. Fig. 1):
November 2001
11
ATV-DVWK-M 206E
Fig. 3:
In smaller and more medium sized plants this strategy, an effective and economic application of precipitant can be realised without additional technical
measuring expense.
November 2001
12
ATV-DVWK-M 206E
Fig. 4:
In order to guarantee the maintenance of the monitoring value for the phosphate concentration (CP) in
the effluent of the wastewater treatment plant the
design value for SPO4 at the measuring site must be
smaller than the monitoring value. That is necessary in order to take into account the P-load which
is contained in the residual suspended matter
which is contained in the effluent. The Pconcentration, which is contained in the solid matter, results from the percentage by mass of the
phosphorus of filterable solids and their concentration in the effluent of the plant:
CP,Part =
mP,SS CXSS
SPO4,des
with:
SPO4,des
CP,MV
CP,Part
F
= CP,MV CP,Part F
(Eqn. 4)
(Eqn. 3)
with:
CP,Part = P-concentration due to residual suspended (in mg/l)
mP,SS = P-contents of dry matter in the sludge (in
mg P/g SS). This value is normally
25 35 mg P/g SS
CXSS = concentration of the filterable solids
(in g/l)
Furthermore an increased factor of safety F to
take into account the resolution effects in the
downstream treatment stages of non-precipitable
phosphate compounds as well as uncertainties in
measurement of the process analysis equipment is
required which, on the basis of operational experience, is to be set at about 0.2 mg/l SPO4.
Thus there results as PO4-P design value for the
regulation of the P-dosing a concentration SPO4,Spec
of:
The quality of regulation can be improved still further through the locking in of the wastewater flow
as influence quantity (comp. Fig. 5). This is particularly interesting with plants with combined biologicalchemical phosphate removal. Here, with hydraulic peaks, resolved phosphate is often displaced in surges from the anaerobic zone into the
aerobic zone. With too short retention times for an
extensive take up of phosphate or with short-circuit
flow, the phosphate concentration in the effluent of
the activated sludge stage can increase very rapidly. This effect can be countered through a disturbance variable compensation depending on the
quantity of water as this affects a timely increase of
the dosing quantity. Attention is to be paid that the
locking in of influencing quantities is so arranged
that, following the start up of a combined wastewater inflow, it remains effective for a certain time
only.
November 2001
13
ATV-DVWK-M 206E
Fig. 5:
Control of the PO4-P concentration with locking in of the influencing quantity of the
wastewater flow
The above presented automated concepts assume that the actual phosphorus concentrations present are available reliably and as far as
possible continuously as measured values. In
order that a failure of the measurement signal,
for example during a calibration or with an
equipment fault is not associated with negative
consequences for the process control, substitutional values must therefore be secured for the
automation which, in place of the real process
values, ensure emergency operation. Furthermore, it is to be defined when the measured
value is to be considered as faulty and, instead
of this, a substitute value is to be applied.
Within the scope of the substitute value strategy it is determined which of the following
processes are to be applied for the creation of
substitute values:
November 2001
14
ATV-DVWK-M 206E
7.1
General
Common precipitants are summarised with their important physical and chemical data in Table 2. Solubility, density and viscosity depend strongly on the
temperature and the substance contents and thereTable 2:
WHC
Percentage by
Prec
Active
subst.
Density or
bulk density
3
Viscosity
Operating
temperature
Iron(III) chloride
Iron(II) chloride
Iron(III) chloridesulphate
Iron(II) sulphate
FeCl3
FeCl2
FeClSO4
Solution (32-42 %)
Solution (20 30 %)
Solution (ca. 40 %)
1
1
1
%
40
20
41
%
13.8
8.7
12.3
g/cm
1.43 (20 C)
1.36
1.52
mPa y s
10 (20 C)
3 (20 C)
42 (15 C)
C
> - 12
> - 15
> - 10
FeSO4 . 7H2O
3 (20 C)
>-2
AlCl3
30
17.8
19.6
6
1.2 (20 C)
Aluminium chloride
Polyaluminium
chloride
Aluminium
sulphate
Sodium aluminate
1.3 (20 C)
10 (20 C)
> - 20
Al(OH)3-xClx
Solution (5-10 %)
5.9 7.5
1.3
10 (20 C)
> -15
Al2(SO4)3
Solution
24
1.27
10 (20 C)
> -15
NaAl(OH)4
Solution (5-12 %)
7.3 11
1.3 (20 C)
20 (20 C) * to
200 ** (20 C)
> - 20
Powder
Powder
1
1
0.8 1.0
0.4
Suspension
(20-40 %)
20
1.1 (20 C)
>0
5 % Al content
11 % Al content
10 % solution; different values through different grain size distribution
Table 3 contains information on the resistance of various material compared with aqueous solutions of
the precipitant.
November 2001
15
ATV-DVWK-M 206E
Tab. 3: Resistance of various materials to aqueous solutions of precipitants at 20 C (1 = good
resistance, 2 = limited resistance, 3 = non-resistant)
Material:
Aqueous solution of:
Iron(II) chloride
Iron(III) chloride
Iron(III) chloride-sulphate
Iron(II) sulphate
Sodium aluminate
Aluminium chloride
Aluminium sulphate
Aluminium hydroxide chloride
Milk of lime
*
**
St 35,
St 37
1.4301
(V2A)
1.4571
(V4A)
GCI*,
NGI**
Titanium
PVCU
HD
PE
GRP
3
3
3
3
1
3
3
3
1
3
3
3
2
1
3
2
2
1
3
3
2
1
1
2
1
2
1
3
3
3
3
1
3
3
3
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
2
2
2
1
1
1
1
1
1
7.2
Dosing Facilities
16
November 2001
ATV-DVWK-M 206E
number of revolutions per minute, piston stroke or
number strokes per minute, with eccentric screw
pumps by the revolutions per minute, with shut-off
devices by the duration of the opening time and
with regulator devices by the degree of opening.
The dosing and circulation pumps should as far as
possible be set up in the vicinity of the storage
tanks, in order to keep the suction lines short. Fundamentally the suction line should be a nominal
width larger than the pressure line. With piston and
piston diaphragm pumps operating behaviour is
improved by pulsation dampers.
With dosing using pumps care is to be taken to
provide a sufficient back pressure on the delivery
side. With several dosing points and different delivery heads the pressure drop is to be taken into account. Therefore appropriate measures, such as
pressuriser valves or separate dosing pumps, are
to be planned. For the layout it is to be noted that
the performance data of the dosing facilities are
Fig. 6:
7.3
November 2001
17
ATV-DVWK-M 206E
The following details are pointed out:
start-up facilities (10,14), which can be replaced by a filling connection for process water
as an alternative (17).
flap trap with strainer basket (16).
overflow valve (22) for the security of the pump
membrane and the pressure side pipeline system.
the delivery flow can be determined using suspended solid particle flowmeters or MIF (24).
with larger plants the continuous registration of
the precipitant flow using MIF is sensible for
operating reasons. At least one container
should be firmly installed for the gauging of capacity in litres in order thus to be able to check
the dosing simply at certain time intervals.
leakage monitoring (29), which indicates leaks
in the dosing station and the pipeline system
and which possibly automatically activates a
Fig. 7:
18
November 2001
ATV-DVWK-M 206E
Attention is drawn particularly to the following:
Fig. 8 shows the necessary equipping for the storage, preparation and dosing of milk of lime as lime
hydrate. In general lime hydrate is delivered in silo
vehicles and transferred into the storage silo (6).
The delivery of precipitant is supported pneumatically via air cushions (5). The blower (2) should, as
far as possible, be mounted directly on the silo. An
automatic monitoring of the cleaning intervals and a
monitoring of the pressure difference of the exhaust
air filters (12) is recommended. The filling level is
monitored using mechanical detectors (7, 8), for
example rotating blades, pivoting forks, or monitored via the silo weight through continuous measurement equipment (15), for example: pressure
pickup. Cellular wheel sluices prevent the shooting of the silo content material and serves as initial
distributors for the downstream spiral conveyer (14)
or container scales. The material is transported via
the spiral conveyor (14) by charge into the batching
and storage tanks (16). The addition of dilution water (13) is controlled via the filling level (19). Normally the silo material, as no high demands have
for accuracy have to be placed on the mass flow, is
added via metering screws proportional to volume.
By means of special structural design, for example
as hollow screw, opposed double-lead screws or as
metering screw with superimposed rotational and
axial movement, a self-cleaning effect is achieved
and encrustation prevented.
November 2001
19
ATV-DVWK-M 206E
Fig. 8:
dosing lines, as far as possible, should discharge below the water level.
ring circuits should always be filled, when idle
with water. Longer pipelines should be flushed
with water on completion of dosing.
connections for the acidulation of the pipeline
system are to be provided.
In addition the requirements from the last three bullet points in Section 7.3.1 are to be considered
analogously.
Below some peculiarities with pourable precipitants
are additionally pointed out:
20
ATV-DVWK-M 206E
sociated heating and an automatic gate valve
below the screw outlet opening should be provided. However, basically, the screw mouth
should be easily accessible in order to be able
to carry out possible necessary cleaning tasks.
7.4
7.5
Economic Efficiency
November 2001
21
ATV-DVWK-M 206E
concentration can, in certain cases, be large due
the varying process behaviour of the biological Premoval. Here, through process control, there is the
possibility of stabilising the biological P-removal
through prevention of a large input of precipitant
and thus indirectly reduction of the requirement for
precipitant and the sludge yield.
Furthermore, it is pointed out that an adaption of
the storage and dosing facilities also contributes to
the economical efficiency of phosphate removal. In
particular with very small plants it is not practical to
install very large storage tanks as here, with complete filling, the precipitant has to be stored too
long. This is to be noted particularly with sodium
aluminate and pourable precipitants. Although
higher costs result with smaller storage tanks and
smaller delivery quantities, the investment costs of
smaller tanks are lower and the operation simpler.
Ordinances, Standard
Specifications and
Standards
[Translators note: References available in English are
shown as such. For those references with no known official translation a courtesy translation is provided in
square brackets]
EN 879
EN 881
EN 882
EN 883
EN 887
EN 888
EN 889
EN 890
22
November 2001
EN 891
EN 935
EN 1189
EN 12255-13
DIN 19 611
DVGW W 622
ATV-DVWK-A 131E
Dimensioning of Single-Stage Activated Sludge
Plants, (2000)
ATV-A 202
Verfahren zur Elimination von Phosphor aus Abwasser [Processes for the Removal of Phosphorus
from Wastewater] (1992)
ATV-DVWK-M 269
Prozessanalysengerte zur Bestimmung von N, P
und C in Abwasseranlagen
[Process Analysis Equipment for the Determination
of N, P and C in Wastewater Systems] (2000)
KVR-Richtlinie [CCC Directive]
Leitlinie zur Durchfhrung dynamischer Kostenvergleichsrechnungen
[Guideline for the carrying out of dynamic cost
comparison calculations], Publ.: LAWA, Kulturbuchverlag Berlin GmbH, ISBN 3-88961-228-8
NN
Verordnung ber Anlagen zum Umgang mit
wassergefhrdenden Stoffen und ber Fachbetriebe (VAwS), lnderspezifisch
[German Ordinance for plants on the handling of
water-hazardous substances and on specialist operation (VAwS), specific for each German Federal
State]
NN
Herstellung, Lagerung und Dosierung von Kalkprodukten
[Production, storage and dosing of lime products];
ATV-DVWK-M 206E
Bundesverband der Deutschen Kalkindustrie e.V.,
Kln (1992), pH-gesteuerte Dosierung von Kalkmilch zur simultanen Phosphorelimination auf
Klranlagen
[pH controlled dosing of milk of lime for simultaneous phosphorus removal in wastewater treatment
plants]
NN
Herstellung und Dosierung von Kalkmilch
[Production and dosing of milk of lime]; Bundesverband der Deutschen Kalkindustrie e.V., Kln (1986)
November 2001
23