Guideline

Cooling Water Guideline

VGB-R 455e
Publisher
VGB PowerTech e.V.

Publishing house
VGB PowerTech Service GmbH
Verlag technisch-wissenschaftlicher Schriften
P.O. box 10 39 32, 45039 Essen, Germany
Phone: +49 201 8128-200
Fax: +49 201 8128-329
E-mail: [email protected]

ISBN 978-3-86875-095-9 (Print)

ISBN 978-3-86875-621-0 (eBook)

www.vgb.org
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Preface
The present Guideline supersedes VGB Cooling Water Guideline VGB-R 455 P, the
first edition of which appeared in October 1990. The present edition has been re-
structured, updated and expanded. The information given is based on the experi-
ence gained in the VGB Working Panel "Chemistry of Water Treatment" from the
operation of main, service and other cooling systems. The editor is unable to accept
any responsibility for the accuracy of the content. The users are themselves respon-
sible for observing any patent and other intellectual property rights that might apply.

The following were involved in preparing and revising this Guideline:

Dipl.-Ing. W. Fichte, Allianz-Zentrum für Technik GmbH, Ismaning

Dr. H.-J. Krabbe, VEW ENERGIE AG, Dortmund
Dipl.-Ing. H.-G. Seipp, ABB ALSTOM POWER, Mannheim
Dr. J. Wasel-Nielen, InfraServ GmbH & Co Höchst KG, Frankfurt am Main
Dr. R. Truppat, VGB-Geschäftstelle, Essen

Our special thanks go to these gentlemen and to all the other members of the
Working Panel who played an active part in the revision of this Guideline.

The editor invites users to submit supplementary information and suggestions for
improvement for incorporation into future editions of the guideline

Essen, January 2000

VGB PowerTech e.V.

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Contents Page

1 Introduction .......................................................................................... 7
2 Cooling procedures.............................................................................. 7
2.1 Once-through cooling with or without outfall cooling............................ 8
2.2 Recirculation cooling in an open circuit ............................................... 9
2.3 Recirculation cooling in a closed circuit ............................................... 12
2.3.1 Recirculation cooling with a surface condenser................................... 12
2.3.2 Recirculation cooling with direct-contact condenser............................ 14
2.4 Recirculation cooling with hybrid cooling tower ................................... 15
3 Cooling water conditioning and treatment............................................ 16
3.1 Once-through cooling systems ............................................................ 16
3.1.1 Water quality........................................................................................ 17
3.1.2 Mechanical cleaning ............................................................................ 17
3.1.3 Treatment with microbiocides .............................................................. 17
3.1.4 Process engineering aspects............................................................... 18
3.2 Open-circuit recirculation cooling systems .......................................... 19
3.2.1 Water quality........................................................................................ 19
3.2.2 Treatment of make-up water................................................................ 19
3.2.3 Conditioning of the circulating water .................................................... 21
3.2.3.1 Hardness stabilisers ............................................................................ 21
3.2.3.2 Dispergents.......................................................................................... 22
3.2.3.3 Corrosion inhibitors .............................................................................. 22
3.2.3.4 Microbiocides ....................................................................................... 24
3.2.4 Process engineering aspects............................................................... 25
3.3 Closed-circuit recirculation cooling systems ........................................ 28
3.3.1 Water quality........................................................................................ 28
3.3.2 Conditioning of the circulating water .................................................... 29
3.3.2.1 Conditioning of generator cooling systems.......................................... 29
3.3.2.2 Conditioning of cooling systems for motors and refrigerating units ..... 29
3.3.3 Process engineering aspects............................................................... 30
4 Materials .............................................................................................. 30
4.1 Materials and cooling water quality...................................................... 31
4.2 Materials and design............................................................................ 34
4.3 Materials and mode of operation ......................................................... 35
5 Monitoring by analysis ......................................................................... 37
5.1 Monitoring by chemical analysis .......................................................... 37
5.1.1 Significance of cooling water analysis parameters .............................. 40
5.2 Microbiological analysis ....................................................................... 44
5.2.1 Investigations ....................................................................................... 44
5.3 Monitoring for corrosion ....................................................................... 45
5.3.1 Investigations ....................................................................................... 45
6 References .......................................................................................... 46

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1 Introduction

This guideline deals with the cooling procedures and technologies commonly used in
power generation plants. It dedicates particular attention to the inter-action between
the cooling water and the components of a cooling system - heat exchangers, piping,
valves, pumps, and possibly cooling towers - under the conditions of the respective
cooling procedure. Condensation in air as a method for cooling turbine steam is not
part of the scope of this guideline.

The pertinent statutory codes and regulations must be observed in all actions taken
to improve the operation of cooling systems, especially with respect to the treatment
and conditioning of cooling water and, as necessary, the discharging of spent water
and effluent.

The conditions applying to discharge into waterbodies are described in the appendi-
ces to the German Waste Water Ordinance dated 31st March 1997. The Waste
Water Ordinance and its appendices replace the General Framework Administrative
Procedure on Minimum Requirements for the Discharge of Effluents into Water-
bodies. The minimum requirements established e.g. in Appendix 31 (Water
Conditioning, Cooling Systems, Steam Generation) of the 31st July 1996 edition of
the General Framework Administrative Procedure continue to apply until such time
as minimum requirements for effluent according to the Waste Water Ordinance have
been defined. These minimum requirements apply unless the local licensing
authority prescribes other standards on special grounds.

2 Cooling procedures

In a power plant, the turbine condenser is the main heat sink with the greatest cool-
ing water demand. Cooling water systems for cooling turbine condensers can in
principle be operated according to three methods which differ in terms of the extent
to which the cooling capacity of the water is utilised and what happens to the heat
removed:
- once-through cooling with or without outfall cooling
- recirculation cooling in an open circuit and
- recirculation cooling in a closed circuit.
Besides the turbine condenser, there are other components in the power plant that
have to be supplied with cooling water. Problems in the form of corrosion or deposits
have occasionally been encountered when such cooling loads are supplied with
freshwater direct from the waterbody or with conditioned cooling tower make-up
water [1]. The state of the art is to combine such secondary cooling loads into closed
circuits operated with demineralized water as initial fill and make-up water. The heat
to be removed from such closed systems is generally passed to the condenser
cooling system via a heat exchanger. The heat exchanger used is subject to the
same criteria as the turbine condenser.

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2.1 Once-through cooling with or without outfall cooling Introduction

When once-through cooling (freshwater cooling) is used, water is taken from a

waterbody (river, canal, lake, sea) via an intake structure, is pumped to the heat
exchangers, passes through the cooling loads once only, and is returned to the
waterbody, possibly via a discharge structure (Fi g u r e 1 ). Almost the entire heat
removed is passed onto the receiving waterbody, which means that once-through
cooling needs a lot of water. At a cooling water temperature rise of, for instance,
10 K, a cooling water flow rate in the order of magnitude of 3.5 m³/s per 100 MW of
installed electrical capacity is required. Technical aids can be used to match the
cooling water flow to fluctuations in the load on the power plant or to the allowable
warm-up of the receiving waterbody, for example by means of variable-trim or con-
trolled-prerotation pumps or frequency converters [2]. In the cold season, a part flow
of the heated cooling water can be returned to the intake structure via a separate
line to ensure that the intake point remains ice-free.

with outffall cooling

turbine cooling tower

without outffall cooling

return pump
C B A
condenser

supply

receiving
A = coarse sreen waterbody
B = fine screen
C = strainer

Figure 1. Once-through cooling (freshwater cooling).

The waste heat input into the receiving waterbody can be reduced by operating the
once-through cooling system with outfall cooling, i.e. the heated cooling water will be
re-cooled in a spray cooling tower before it is discharged into the waterbody. At the
same time, the intensive mass transfer between the water and the air enriches the

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oxygen content in the air, which is a desirable side effect because there is frequently
an oxygen deficit in surface waters. Some slight evaporation and spray losses occur
as the water passes through the outfall cooling tower.

Once-through cooling systems operated with an outfall cooling tower normally by-
pass the cooling tower as long as the water level and the temperature of the receiv-
ing waterbody permit the entire waste heat to be discharged. Outfall cooling has to
be taken on line if the temperature of the receiving waterbody approaches the al-
lowable limit or if the authorities call for oxygen enrichment of the cooling water.
Intermittent operation of an outfall cooling tower makes the cooling tower internals
particularly prone to clogging due to deposits. For this reason, special attention must
be paid to the suspended solids in the cooling water (see Section 3.1.2).

2.2 Recirculation cooling in an open circuit

In an open-circuit recirculation cooling system, the water is re-cycled via a cooling

tower, in which the waste heat is discharged to atmosphere (Fi g u r e 2 ). In the cool-
ing tower, direct heat exchange between the water and the air takes place, which is
particularly effective because heat of evaporation is extracted from the system as
well. As a result of evaporation, the circulating cooling water will be concentrated,
which is tolerable only to a limited extent and requires blowdown. The blowdown
water and the evaporation and spray losses, which altogether should normally not
exceed 2 % of the recirculation flow per hour, have to be replaced.

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evaporation

turbine

cooling tower
make-up water
return

condenser

supply
pump

blowdown

Figure 2. Recirculation cooling in an open circuit (wet re-cooling).

The make-up water requirement (MU), evaporation and spray losses (E), blowdown
(BD) and the concentration factor (C) are correlated with each other according to the
following functions:

MU
MU = E + BD C = BD

E·C E
MU = C - 1 BD = C - 1

Evaporation, which depends on many climatic factors and the technical design of the
cooling tower, can be approximated by means of the following formula:

E = f · U · ∆T

in which
-1
f = so-called "climate factor" in K ,
3
U = circulating water mass flow in the circuit in m /h,
∆T = temperature difference between supply and return lines in K.

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In Central European latitudes, 1.1 to 1.5 % evaporation relative to the circulating

water mass flow at a ∆T of 10 K can be considered normal [3], [4]. The amount of
make-up water required depends essentially on the concentration factor. Low
concentration factors lead to a super-proportional make-up water requirement.
F i g u r e 3 illustrates the correlations using the example of a 1000 m³/h circuit.

60
Zusatzwasser Z
make-up water MU Abflut A BD
blowdown Ve rd unstung VE
evaporation
50

40
[m³/h]

30

20

10

0
1 2 3 4 5 6 7 8 9 10
Eindickung
concentration E C
factor

Figure 3. Correlation between make-up water requirement, blowdown, evaporation, and

concentration factor in service, taking the example of a 1000 m³/h open
recirculation cooling circuit.

At higher concentration factors, which represent a higher risk of solids precipitation

and corrosion attack, the make-up water requirement drops sub-proportionally.

In recirculation cooling in an open circuit, the water quality can be enhanced by

treating the cooling tower make-up water and/or conditioning the water in the circuit.
This makes it possible to keep the concentration factor and thus the make-up water
requirement within certain limits that can be chosen depending on the quality of the
raw water available and the treatment and/or conditioning procedures used (see
Sections 3.2.2 and 3.2.3).

The make-up water input point into the circuit depends largely on the treatment
procedure used and the properties of the make-up water (see Section 3.2.4). To
prevent wide fluctuations in the concentrations of the substances contained in the

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circulating water, make-up water addition and blowdown should be performed in a

controlled fashion (uniformly) as far as possible.

2.3 Recirculation cooling in a closed circuit

In recirculation cooling in a closed circuit, the water is permanently re-cycled. Unlike

in open-circuit recirculation cooling, the cooling water is continuously recirculated in
a closed system, and the heat is discharged to the atmosphere indirectly via heat
exchangers. Since there is no evaporation, there is no concentration factor and thus
there are no losses due to evaporation and salts blowdown. The closed system is in
principle loss-free, so that it can be economically operated with demineralized water
as the initial fill and make-up water (see Section 3.3.1). Cooling water losses, e.g.
through unsuitable shaft seals at the pumps, should be avoided (see Section 3.3.3).

2.3.1 Recirculation cooling with a surface condenser

F i g u r e 4 shows a schematic representation of a turbine condenser cooling system

of the type described. The turbine exhaust steam is condensed in a water-cooled
surface condenser, as in the case of once-through cooling or open-circuit recircula-
tion cooling. The cooling water is circulated in a closed system between the con-
denser and the cooling tower, in which it is air-cooled in cooling elements.

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turbine

return

condenser

supply
pump

Figure 4. Recirculation cooling in a closed circuit (dry re-cooling) - surface condenser.

The closed-circuit recirculation cooling principle using demineralized water as initial

fill and make-up water is also used for the secondary and intermediate cooling cir-
cuits referred to earlier and for cooling the generator windings. These circuits are
indirectly cooled via the turbine condenser cooling water or with air in heat ex-
changers (F i g u r e 5 ) [5].

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turbine condenser cooling system

surge tank intermediate heat

exchanger
N2
secondary cooling load
pump

Figure 5. Recirculation cooling in a closed circuit - simplified schematic diagram of a inter-

mediate cooling system.

2.3.2 Recirculation cooling with direct-contact condenser

In a turbine condenser cooling system with a direct-contact condenser, the turbine

steam is condensed by injecting a part flow of the condensate circulating between
the cooling elements in the cooling tower and the condensate pump directly into the
condenser steam space (F i g u r e 6 ). The condensate is air-cooled in the cooling
tower [6], [7].

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turbine

return

condenser
supply
pump

Figure 6. Recirculation cooling in a closed circuit (dry re-cooling) - direct-contact condenser.

2.4 Recirculation cooling with hybrid cooling tower

Hybrid cooling is a combination of wet and dry cooling (F i g u r e 7 ). In recirculation

cooling with a hybrid cooling tower, the turbine steam is condensed as described in
Section 2.2 or Section 2.3.1. To intensify the cooling effect, the previously air-cooled
cooling water from open-circuit recirculation cooling is passed through the cooling
elements in the cooling tower. The heat is removed to the atmosphere in the same
way as in Section 2.2 [8], [9], [10], [11].

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evaporation

turbine

cooling tower
make-up water
return

condenser

supply
pump

blowdown

Figure 7. Recirculation cooling with a hybrid cooling tower

(open circuit - wet and dry re-cooling).

3 Cooling water conditioning and treatment

3.1 Once-through cooling systems

In principle, all kinds of water available in adequate quantities - such as seawater,

brackish water, river water and water from inland lakes, including bank-filtered water
- can be used for once-through cooling. Large mass flows and direct discharge of the
heated cooling water into the receiving waterbody as a rule do not permit chemical
treatment or conditioning. Thus, actions to improve the water properties are normally
limited to reducing the amounts of undissolved substance and microbiological
growth and possibly to actions to promote the formation of a protective layer on the
system materials. Outflow cooling can be used to reduce the heat input into the
receiving waterbody, while intensive aeration in the cooling tower helps to improve
the quality of the discharged water. Concentration factor due to evaporation is
minimal (a factor of about 1.05). Lime precipitation is possible if a part flow of the
outflow water is re-cycled.

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3.1.1 Water Quality

The types of water that can be used for once-through cooling contain undissolved
and dissolved substances in widely different quantities. The undissolved substances
include coarse dirt such as flotsam, tree trunks, branches, leaves, grass, etc. and
suspended solids such as sand, clay, dead macro- and micro-organisms. The
substances dissolved in the water comprise mainly salts of the alkaline metals
sodium and potassium and of the alkaline earth metals calcium and magnesium.
Also the gases oxygen, nitrogen and carbon dioxide and in lesser amounts heavy
metal salts, organic substances such as detergent and cleaning agent residues, and
ammonium salts. Coastal seawater, especially, may also contain hydrogen sulphide.

Both the undissolved and the dissolved substances may vary widely depending on
the time of year, the temperature, the water level in the waterbody, various effluent
discharges, and the tides in the case of seawater and brackish water. The maximum
concentrations of the water contents should be taken into account in the planning for
the plant.

3.1.2 Mechanical cleaning

Surface water must be mechanically cleaned to protect the once-through cooling

system against coarse dirt, suspended solids and macro-organisms. As a rule,
mechanical cleaning is performed in a number of stages, with coarse, medium and
fine screens catching the flotsam and driftings. If the water is very sandy, a settling
tract (mole, basin) may have to be provided downstream of the screens to prevent
erosion corrosion of the metal surfaces; the size and geometry of the settling tract
must be determined in accordance with the sedimentation speed of the abrasive
solids.

Suspended substances that get past the fine screen are separated out by travelling
screens. Instead of these screening devices, which form part of the intake structure,
filter vessels may be used immediately upstream of the heat exchangers. These
have proven particularly effective against seaweed and heavy mollusc growth. All
screening facilities are equipped with backwash systems which come into action at a
pre-determined differential pressure. These facilities also have a safety feature to
protect them against excessive differential pressure; if this safety feature trips,
contaminated water may enter the cooling systems. To prevent corrosion damage to
the heat exchanger tubes, the cooling systems must be cleaned by hand after each
such ingress.

3.1.3 Treatment with microbiocides

Especially when seawater or brackish water is used for cooling, an explosion of the
macro-organism and micro-organism population can lead to critical operating
conditions. For instance, macro-organisms may block the passage of tube cleaning
balls, and micro-organisms may impair heat transfer in the heat exchanger tubes by

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forming a biofilm on the tube surface. Also, organisms can cause corrosion damage
to copper-based alloys and stainless steels.

To prevent these adverse effects, microbiocides are added to the cooling water. The
most commonly used microbiocides are chlorine gas, chlorine bleach and chlorine
dioxide. Their effect is based on the formation of hypochloric acid in the aqueous
medium. In cooling waters with a higher pH (>8.5) the less effective hypochlorite ion
-
(OCl ) is formed. Oxidizable substances in the cooling water, such as organic
compounds. sulphides, ammonia, etc. likewise react with the microbiocide, so this
must be taken into account in the determination of the dosage required. Intermittent
injection is most effective, but continuous dosing is also possible.

If continuous dosing is used, a free chlorine content of 0.1 mg/l in brackish water or
about 0.25 mg/l in seawater is generally sufficient for adequate protection of the
cooling system. Mollusc larvae can be destroyed by continuous chlorination with
0.5 mg/l Cl2 or by intermittent chlorination with 2 to 3 mg/l for one hour at a time at
intervals of four to six hours. If mollusc growth is present, higher chlorine
concentrations of around 10 mg/l will be needed and must be maintained for several
days [12].

The following must be observed if treatment with chlorine or chlorine compounds is

used:
− seasonal fluctuations in temperature affect the amount of microbiocide needed
− high chlorine doses promote corrosion attack on copper alloys and stainless
steels
− the applicable water resources management regulations must be observed (see
Section 1)
− if microbiocide treatment is interrupted for an extended period, there is a danger
of irreversible growth forming that can only be removed by mechanical means.

3.1.4 Process engineering aspects

To prevent deposits and formation of biofilm, the heat exchanger tubes should be
continuously cleaned by means of travelling balls; the balls must be monitored for
wear and replaced in good time. If a clinging deposit has formed on the inside of the
tubes, it may be necessary to operate the tube cleaning system with abrasive balls
for a time.

The microbiocide is as a rule added at the intake structure, and the dosing points
should be arranged to ensure a uniform distribution. The microbiocide concentration
must be monitored.

From case to case, ferrous sulphate may be added to promote the formation of a
protective surface layer on copper-based alloys. Useful information for process
engineering is given in the literature [13], [14] and [15].

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Protective measures to be adopted during downtimes are described in the VGB

guidelines for tube materials [16] and [17].

3.2 Open-circuit recirculation cooling systems

In open-circuit recirculation cooling systems, evaporation of the circulating water

causes the concentration of the undissolved and dissolved substances in the water
to build up, i.e. the substances entering the system in the make-up water
accumulate. Also, gases and solids washed out of the cooling air are entrained in
the circulating water. These conditions - and the heat stored in the heat exchangers -
promote the precipitation of suspended and originally dissolved solids, micro-
biological growth, impaired heat transfer, and corrosion attack. The various problems
involved may interact to intensify each other: e.g. corrosion including micro-
biologically induced corrosion (MIC [18], [19]) under deposits, formation of biofilm on
rough surfaces of deposits and corrosion products.

3.2.1 Water quality

Of importance in this context are the substances contained in the water that, as a
result of concentration build-up and rising temperatures, can exceed their solubility
point and form insoluble substances. These include the alkaline earth carbonates
and phosphates and, more rarely, the alkaline earth sulphates and silicates.

The corrosive effect of re-cooled water on non-stainless steel is generally enhanced

by the build-up of salts and dissolved gases (oxygen, carbon dioxide). Chlorides are
significant in that they promote corrosion of stainless steels. Sulphates can cause
corrosion of concrete [20]. If complexing substances are present in the water intake,
they can adversely affect the formation of the oxide layer especially on copper
materials [21].

Ammonium, phosphates and nitrates contribute to the nutrient supply for biological
growth.

3.2.2 Treatment of make-up water

Since the water is re-cycled within the open circuit, much less raw water is required
than for once-through cooling. In large recirculation cooling systems, however,
considerable amounts of water are still needed to make up for the evaporation and
blowdown losses. This makes it impossible to completely eliminate all the
substances contained in the raw water that could cause trouble in the cooling
system. Treatment must be limited to eliminating or at least reducing the substances
with the greatest interference potential, first and foremost the mechanical
contaminations and the hardness hydrogen carbonates that are inclined to form lime
deposits [22], [23], [24].

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Course mechanical cleaning of surface water from rivers and lakes is the same as
for once-through cooling (see Section 3.1.2).

Before the raw water goes on for further treatment or use, it is usually subjected to
fine cleaning by filtration through sand or gravel or by flocculation followed by
sedimentation. These procedures significantly reduce the residual suspended solids
content. Well water and bank-filtered water do not require coarse mechanical
cleaning but must be aerated or percolated if they contain major amounts of carbon
dioxide, iron or manganese. In these processes, the carbon dioxide is expelled and
the oxygen content raised. At the same time, iron and manganese are oxidated into
practically water-insoluble oxide hydrates that can be separated out in downstream
filters. The removal of iron and especially manganese is as a rule microbiologically
enhanced by specially adapted bacteria at the filter surface.

As already mentioned, the chemical treatment of raw water for use as cooling tower
make-up water in large-scale systems is usually limited to decarbonation, which is
generally performed with acid or lime, but in special cases also in weakly acidic
cation exchangers. Decarbonation by means of dosing of the water with acid, usually
sulphuric acid, involves replacing the hydrogen carbonates that are of interest here
by sulphates:

H2SO4 + 2 HCO3 → 2 CO2↑ + 2 H2O + SO4

2-

By contrast, decarbonation by means of lime (hydrate) also removes the alkaline

earth carbonates from the water. The total salts content and the concentrations of
calcium and magnesium ions are reduced accordingly:

Me"(HCO3)2 + Ca(OH)2 → Me"CO3↓ + CaCO3↓ + H2O

Hydrogen carbonates lend the circulating water a certain buffer capacity against
influences that would tend to reduce the pH and that come about for example due to
induction and washing out of acid gases in the cooling tower or as a consequence of
biological processes. Moreover, the hydrogen carbonates of calcium and
magnesium are involved in the formation of corrosion-inhibiting layers on steel
surfaces. Thus, regardless of the procedure used, decarbonation should be
performed only to the extent required to leave a residual content of between 0.5 and
1 mmol/l hardness hydrogen carbonate, corresponding to 1 to 2 mmol/l hydrogen
carbonate, in the circulating water. This also applies to subsequent correction of the
pH value or the hardness hydrogen carbonate by dosing the circulating water with
acid. Excessive decarbonation enhances the corrosion risk for low-alloyed steel and
also for copper alloys [25], and beyond the limit recommended here it increases the
probability of calcium carbonate precipitation at the heat exchange surfaces. If
hardness stabilisers are added, higher values may be tolerable.

[26] identifies features of decarbonation procedures and conditions for their use
under which one procedure or another may be more suitable for a given application.
Among the selection criteria, the question of how to dispose of the effluent and solid
residues is going to become increasingly important [27], [28].

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3.2.3 Conditioning of the circulating water [12], [29], [30], [31], [32], [33], [34],
[35], [36], [37], [38], [39]

Interference with cooling operations due to the behaviour of the substances

contained in the water under the conditions prevailing in the cooling system and the
resulting material attack should be prevented or eliminated primarily by means of
process engineering measures, by choosing suitable materials, and by adapting the
operating mode. In some cases problems involving deposits and corrosion can also
be kept in check by conditioning the circulating water.

Hardness stabilisers, dispergents, corrosion inhibitors and microbiocides may be

used for conditioning purposes. These cooling water treatment agents are also
available in combination products, the advantages of which lie in their higher
efficiencies, broader spectrum of activity and easier handling by comparison with the
individual products. However, there are not yet any standard procedures for
objectively monitoring the efficacy of such conditioning agents. Highly complexing
hardness stabilisers and dispergents can affect the formation of surface oxide layers
especially on copper/zinc alloys. For this reason, these conditioning agents should
not be used in heat exchanger made of these materials, at least during their first
weeks in service. These limitations do not apply to stainless steels or titanium.

Conditioning agents, especially microbiocides and corrosion inhibitors, may have an

adverse effect on the receiving waterbody when discharged with the blowdown water
[40]. Use of conditioning agent is permissible only subject to observance of the
restrictions imposed under water resources management regulations and the
conditions of the applicable use-of-water licences (see Section 1).

In the large cooling systems of modern power plants, whose supply and return lines
are protected or, given the composition of the water, are not susceptible to corrosion
attack, and equipped with condensers made of stainless steels or titanium, use of
corrosion inhibitors is not necessary.

3.2.3.1 Hardness stabilisers

Hardness stabilisers are intended to prevent the precipitation of salts of the

hardness ions due to transgression of the solubility product threshold (scaling). The
formerly commonly used polyphosphates have nowadays been replaced by
phosphor-organic compounds on the basis of phosphonic acids and more and more
by non-phosphorous polymers and co-polymers (see Section 3.3.3.2). By contrast
with stoichiometric complexants, these are already effective in sub-stoichiometric
quantities to stabilise precipitation-prone substances to such an extent that they do
not precipitate (threshold effect). The stabiliser is chemisorped on the surface of e.g.
calcium carbonate crystals to inhibit further growth of the crystals for some time. The
concentration required depends not only on the composition of the cooling water but
also on circuit-specific parameters such as dwell time, contact time, and tube wall
temperature in the heat exchangers. Following decarbonation, it is usually sufficient
to add hardness stabilisers in low doses to prevent the residual hardness (up to
4 mmol/l hydrogen carbonate) from precipitating out. However, high-performance

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formulas in high doses (all organic treatment (AOT) (see Section 3.2.3.3)) are also
capable of stabilising much higher hardness former contents: up to hydrogen
-
carbonate contents of c(HCO3 ) = 10 mmol/l at calcium contents of up to
2+
c(½ Ca ) = 28 mmol/l. It is very difficult to establish a general rule here, as all the
chemical parameters of the water have to be taken into account.

3.2.3.2 Dispergents

Dispergents prevent the solids contained in the circulating water from coagulating
and settling, so as to keep them in suspension. Most dispergents are synthetic low-
to medium-molecular polymers, such as polyacrylates, co-polymers of acrylic acid
and methacrylic acid or of acrylic acid and acrylic acid methyl ester, with molar
masses between 1,000 and 20,000 g/mol. Adsorption of the dispergents on the solid
particles imparts a like electric charge to these, to that they repel each other and
remain in suspension. Anionic polymers are preferably used. (The mechanism of
dispersion - influence on the zeta potential - and of hardness stabilisation via the
threshold effect - steric hindrance of agglomeration due to surface occupation - are
theoretical borderline cases that make it very difficult to distinguish between
hardness stabilisation and dispersion in phenomenological terms.) Dispergents may
synergetically intensify the action of hardness stabilisers, corrosion inhibitors and
microbiocides and are thus present in nearly all combination products. They are of
particular importance in combination with corrosion inhibitors, as they keep the
surfaces to be inhibited free from deposits. If continuously added, preferably in
combination products, the application concentration of dispergents is normally less
than 10 mg/l in the circulating water. If discontinuously added, the dose is 100 to
200 mg/l.

A further category of dispergents is based on surface-active substances, tensides,

that are frequently used to prevent organic deposits (fouling) and as a back-up for
microbiocides. Only low-foaming tensides whose decomposition behaviour does not
significantly increase the biological activity of the circulating water are suitable for
use in cooling systems.

3.2.3.3 Corrosion inhibitors

Corrosion inhibitors are intended to give active protection against corrosion to

reduce corrosion attack on the materials - especially low-alloyed steels - by the
cooling water.

Inhibitors build up more or less solid protective layers or actively stop the corrosion
process by intervening in the chemical reaction.

For the purposes of conditioning open-cycle cooling systems, a distinction is made

between an acid mode (pH value < 7), a neutral mode (pH value 7 - 8), and an
alkaline mode (pH value > 8) of operation. The higher the pH value, the slower the
corrosion reaction in iron, copper and their alloys usually takes place, since the
cathodic reaction of the oxygen-induced corrosion that usually prevails here

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O2 + 2 H2O + 4e ↔ 4 OH
- -

is controlled by the pH value. On the other hand, the higher the pH value, the greater
becomes the danger of deposits especially of calcium carbonate and calcium
phosphate or slightly soluble zinc salts, so that neutral and alkaline conditioning is
always performed in combination with hardness stabilisers and/or dispergents. In the
acid and neutral modes, ortho-, polyphosphates and/or zinc salts are used as
inhibitors against corrosion of iron. Orthophosphates are attributed a primarily anodic
action (3 Fe + 2 PO4 → Fe3(PO4)2↓), zinc salts a cathodic action (Zn + 2 OH-
2+ 3- 2+

→ Zn(OH) 2↓). Polyphosphates take effect - also due to hydrolysis to ortho-

phosphate - in the anodic, but also in the cathodic corrosion sub-step. Apart from
being directly involved in the corrosion processes, inhibitors may also act to reduce
corrosion via the formation of phosphate, zinc oxide or ferrous/ferric oxide protective
layers. In the formation of protective layers, however, it is important to ensure that a
tight cover is formed and that no pitting/crevice corrosion takes place beneath the
layer.

The all organic treatment mode (AOT), which is counted as an alkaline mode,
promises highly reliable protective layers in many waters, as the addition of special
phosphonates and/or polymers allows a very stable and yet thin ferrous/ferric
protective layer to build up [22], [23].

Film-forming inhibitors (as a rule long-chain amines in combination with

phosphonates and/or polymers), that are currently experiencing a certain
renaissance, are particularly susceptible to erosion attack and should thus be used
only under suitable control.

The acid mode with relatively high doses of corrosion inhibitors and acids is now less
frequently used. The neutral mode features moderate dosage rates by comparison.
The alkaline mode calls for significantly higher additive doses but does not require
the addition of acids for pH control. The alkaline mode manages with little or no
phosphor compounds but contains considerable quantities of dispergents.

Corrosion attacks on copper materials are to be feared mainly if the copper oxide
protective layer is deficient or if its primary build-up has been disturbed. Higher pH
values tend to reduce corrosion. On the other hand, complexants, ammonium
compounds or ozone [41] enhance corrosion. If a copper inhibitor has to be used,
this is usually added in the form of organic triazoles (most commonly tolyltriazole
TTA). In this case, attention must be paid to the manner and amount of dosing
required to obtain long-term protection. The inhibitors work best if a metallic clean
surface has been established beforehand.

In cases of copper corrosion, a special watch must be kept on deposits, under which
microbiologically-induced corrosion (MIC) may be present.

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3.2.3.4 Microbiocides

Use of microbiocides may be necessary to combat microbiological growth and its

consequences [42]. Because of their temperature and pH conditions and the
availability of growth-promoting nutrients, open-circuit cooling systems often provide
ideal conditions for the propagation of micro-organisms. The best possible
environment for microbiological growth is to be found in blocked tubes. Micro-
biological growth should primarily be prevented by keeping the systems clean and by
avoiding stagnation zones and deposits, in and beneath which micro-organisms can
house and multiply. A further prophylactic measure is to keep the nutrient supply low
by avoiding and, if necessary, immediately removing organic contaminations. If
biological fouling nevertheless occurs in the cooling circuit, it can be eliminated by
treatment with microbiocides, which, depending on their nature, have different
effects on the growth of micro-organisms.

Some microbiocides effect the permeability of the cell walls, thus intervening in the
life processes of the organisms. By reducing the permeability of the cells, surface-
active agents impair the intake of nutrients and the excretion of waste products;
cationic surface-active microbiocides react with negatively charged ions bonded to
the cell walls, while anionic surface-active microbiocides first reduce the permeability
of the cell and then proceed to dissolve the cell membrane. Organic sulphur
compounds inhibit the metabolic reactions between enzymes and substrate.
Oxidising microbiocides destroy the protein groups and prevent normal enzyme
activity, so that the cell dies.

For ecological reasons, the oxidising agents are predominantly used in open-circuit
cooling systems, chlorine and bromine- and chlorine-releasing compounds and,
more recently, ozone being most commonly used [43], [44], [45]. Chlorine and
chlorine-releasing products are increasing coming in for criticism because they give
rise to chloro-organic compounds. Trials are currently in progress on the use of
hydrogen peroxide, also in combination with other additives [46].

The amount of microbiocide required depends essentially on the contact time, the
pH value and the water temperature, but it may also be subject to an upper limit. For
example, a threshold of 2 mg/l of free chlorine should not be exceeded, as there is
otherwise a danger of corrosion to stainless steels and copper alloys. The
effectiveness of chlorination declines as the pH value rises, as at pH values above
8.5 there are practically only hypochlorite ions present.

The tendency of the micro-organisms to develop a resistance to the microbiocide is

less pronounced if it is added intermittently rather than continuously. The dosing
intervals must be defined with allowance for factors such as the time of year, the
biological burden of the air drawn in by the cooling tower, the quality of the make-up
water, and the operating conditions of the cooling system. Discharge of significant
quantities of free chlorine into the receiving waterbody can be avoided if the
blowdown is closed during dosing and until the free chlorine in the circulating water
has largely been depleted [47].

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The use of microbiocides in recirculation-type cooling systems is regulated in terms

of the maximum allowable residual toxicity in the blowdown water by the minimum
requirements established in Appendix 31 to the General Framework Administrative
Procedure on Minimum Requirements for the Discharge of Effluents into Water-
bodies (see Section 1). An adequate depletion time can be achieved e.g. by closing
off the blowdown.

Large power plant cooling towers should be designed and operated with allowance
for the influences identified above, so that it is not necessary to use microbiocides
on a regular basis.

3.2.4 Process engineering aspects

The structural design of a cooling system and its components and the conditions
under which it operates play an essential role in coping with the specific problems of
open-circuit recirculation cooling systems. Disturbances in cooling operations can be
avoided not only by resorting to chemical intervention but also by process
engineering measures and possibly by the choice of suitable materials (see Section
4). Options for ensuring trouble-free operation by means of chemical agents are
treatment of the make-up water (see e.g. [48]) and conditioning of the circulating
water. Process engineering measures focus primarily on keeping the tube surfaces
clean by means of continuously or intermittently operating tube cleaning systems
and on removing suspended contaminations from the circulating water by filtering a
bypass flow - up to 5 % of the hourly recirculation rate - generally by means of gravel
filters. Cooling water filters upstream of the turbine condenser have proved useful for
preventing tubes from becoming blocked by fragments from the cooling system or
foreign bodies from the cooling tower region. If conditioning agents are added,
attention must be paid to repercussions on the inhibition and stabilization
mechanisms and to adsorption at the filter surfaces.

Ta b l e 1 is a decision-making aid to the alternative use of tube cleaning systems,

bypass flow filters or dispergent. It does not make allowance for the structure of the
solids, which may also be responsible for some problems (deposits, erosion
corrosion).

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Table 1: Options to be used depending on the solids content of the cooling water.

Preconditions
- solids content mg/l <5 < 15 < 15
- flow velocity m/s > 0.5 > 1.5 > 1.5
alternative measures
- continuous tube not necessary, since recommended necessary
cleaning solids content low,
not possible at flow
velocities < 1.5m/s*
- bypass flow filtration not necessary, since recommended necessary
solids content low, (not necessary if
continuous tube
cleaning and
dispergents are
used)
- use of dispergents recommended recommended recommended
(not necessary if
continuous tube
cleaning and bypass
flow filtration are
used)

*) if the tube cleaning system is modified, flow velocities < 1.5 m/s are also possible

With a view to minimising or re-cycling the blowdown, "side-flow treatment" by

means of a diaphragm process is also under discussion [6], [36], which may be
expedient especially in regions that are short of water.

The nature of the make-up water treatment should be taken into account in the
choice of location for feeding the make-up water into the cooling circuit; it may also
be necessary to take special measures on the materials side.
− Use of mechanically cleaned water only as a rule places no restrictions on the
choice of feed-in point.
− Make-up water decarbonated by means of lime can be introduced directly into
the cooling tower basin. Problems may be experienced if the water has
previously been used in the heat exchangers of secondary cooling loads. An
elevated corrosion risk, especially to low-alloyed steels, as a result of calcium
carbonate precipitation due to delayed reactions in the heat exchangers has
been observed [49]. This can be prevented by adding acid to the water that has
been decarbonated with lime; on the other hand, this releases carbon dioxide,
which causes corrosion of unprotected carbon steel and copper-based alloys. If a
corrosion inhibitor is used to condition the circulating water, it may be
advantageous to add the conditioning agent already to the make-up water.
− Water decarbonated by injecting mineral acid or decarbonated in weakly acidic
cation exchangers likewise contains free carbon dioxide and should be passed
via a degasifier or into the circulating water on the way back to the cooling tower.
Components coming into contact with such make-up water must be made of
acid-proof materials or be provided with a protective coating. The same applies in

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cases where the make-up water has been decarbonated by means of the
flocculation/precipitation method. In this process, the concentration of hardness
hydrogen carbonate can drop so far below 1 mmol/l that no protective layer forms
on steel surfaces and the buffer capacity of the make-up water and circulating
water is lost. Pitting corrosion may then occur in copper materials.

The conditioning agent feed-in points should be chosen to ensure rapid and
complete mixing with the circulating water. As a rule, this will be the case if the
conditioning agent is introduced upstream of the cooling water pumps.

The introduction of conditioning agents, which has nowadays been optimised and
requires only very low quantities, calls for the observance of certain process
engineering conditions:
− Adequate but not excessively high flow velocities so that enough conditioning
agent can always be introduced but on the other hand there is no danger of the
formation of the protective layer being impeded by erosion. For reasons
explained earlier, it goes without saying that the agent may not perform properly
in stagnant water during outages or in dead-end lines. A flow velocity range of
between 0.5 and 3 m/s should be assured at all timed.
− The material temperature on the cooling water side of the heat exchanger should
be adequately below boiling temperature, as boiling processes interfere with the
inhibition and stabilization mechanisms. In this context, it should also be
remembered that the boiling temperature drops with falling pressure.

To protect the heat exchanger tubing from clogging due to coarse dirt entrained into
the recirculation system via the cooling tower or fragments from the cooling tower
internals, it has proven expedient to provide screens at the suction side of the
turbine condenser cooling water pumps.

Continuous-action tube cleaning systems need an adequate flow velocity to prevent

the cleaning bodies (balls, brushes) from sticking in the tubes. The type of balls used
- sponge, granulate, polishing or abrasive balls - is important not only to the success
of the cleaning procedure. Attention must always be paid to how they interact with
anti-corrosion protective layers, as otherwise deposits may lead to secondary
corrosion.

The problems involved (preventing deposits, restoration, repair of protective layers)

and the operating conditions (materials, type of conditioning, cooling water flow,
process engineering) influence the choice of ball type and of the hardness and
diameter of the balls. Microbiological slime coatings on titanium condensers are best
removed by balls coated e.g. with corundum, pumice stone or hard plastic granulate.
Polishing balls made of india-rubber/pumice mixtures can be used for example to
compact voluminous foreign-oxide layers in non-ferrous-metal condensers, while
corundum balls can be used to remove clinging deposit layers.

The correct choice of design and backfits, of process engineering solutions and of
conditioning for recirculation cooling systems is essential to trouble-free and cost-
optimised operation.

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3.3 Closed-circuit recirculation cooling systems

By definition, these recirculation cooling systems should be absolutely leak-tight to

atmosphere. However, in larger systems, in particular, some leakage may occur at
valves and pump glands. This leakage should be kept to a low level, as otherwise
the constant input of oxygen-rich make-up water can change the equilibrium of the
circulating water such that corrosion conditions deteriorate.

3.3.1 Water quality

As a rule, demineralized water is used for the initial fill and as make-up water.
However, a condensate that has been cleaned in an ion exchanger or the
condensate from a turbine condenser is also suitable for use. The quality of the
circulating water may deteriorate due to foreign substances present as
contaminations in the cooling system or that penetrate the system from the outside,
e.g. gases from the atmosphere or electrolytes from saline leakage water from the
re-cooling system. As a result, elevated corrosion rates may be experienced
especially on non-alloyed steel surfaces and can lead to a rise in the solids content.
Corrosion products and other solids deposited on the heat exchanger tubing impair
heat transfer. The cooling performance of the heat exchangers may also be
adversely affected in the event of an oil leak into the cooling circuit [50], which may
promote microbiological growth and thus trigger microbiologically-induced corrosion
(MIC).

Ta b l e 2 defines recommended qualities for the circulating water in closed-circuit

cooling systems to ensure trouble-free cooling operation.

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Table 2: Properties of circulating waters in closed-circuit cooling systems.

Parameters Recommendation
Conductivity at 25 °C µS/cm < 30
Conductivity at 25 °C downstream of strongly µS/cm <5
acidic sampling cation exchangers
pH value at 25 °C >7
Oxygen mg/l < 0.020
Oil mg/l <1

3.3.2 Conditioning of the circulating water

Conditioning is not necessary if the conductivity and pH value are in line with the
recommendations in T a b l e 2 . In large, highly ramified cooling systems with various
material combinations, the circulating water must be conditioned to prevent
corrosion. Commonly used conditioning agents are ammonia and soda lye. In
cooling systems that form part of a water/steam cycle, the same conditioning agent
as in the water/steam cycle should be used. It is common practice to use alkaline
conditioning agents to establish pH values between 9.0 and 9.5. If cooling elements
made of aluminium are used, only lower pH values of not more than 8 are
admissible.

3.3.2.1 Conditioning of generator cooling systems

The special requirements of cooling systems for water-cooled generators with high
power ratings make stringent demands on the quality of the circulating water. The
crucial parameter is the direct conductivity, with an allowable maximum limit of
1.5 µS/cm at 25 °C. The pH value and oxygen content are significant factors
determining the corrosion rates of the copper used as the conductor material.
Dissolved copper (pH value < 7.0) can cause electrical bridging due to galvanic
deposition in the rotor winding insulation and can thus reduce the dielectric
resistance of the rotor. If cupric oxide is precipitated out of the super-saturated
condition in turbulence zones, it can impede or block the cooling water flow at the
stator windings. Plant-specific operating modes have been developed in practice to
avoid copper and cupric oxide deposits [51].

3.3.2.2 Conditioning of cooling systems for motors and refrigerating units

The water used as the circulating cooling water for these systems normally contains
some salts (drinking water quality). Conditioning is performed using combination
products containing corrosion inhibitors and, if necessary, anti-freeze compounds.
Water analyses must be performed at regular intervals to check the efficacy of the

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conditioning agents. It may also be necessary to perform microbiological analyses.

Stagnant conditioned make-up water must be stored inaccessible to air, as
otherwise aggressive products may be formed from the decomposition of corrosion
inhibitors.

3.3.3 Process engineering aspects

Surge tanks in closed-circuit recirculation cooling systems must be sealed against

ingress of air by means of a diaphragm or a controlled inert gas (nitrogen) cushion
and must be adequately protected against overpressure and excessive vacuum by
means of suitable safety features (vent facility, safety valve, rupture disc, pressure
compensation loop, vacuum breaker).

If the electrolyte or solids content in the circulating water rises, the following counter-
measures may have to be taken:
− on-line blowdown of the system (particularly effective for removing solids, as
these are kept in suspension; but high water consumption)
− partial drain-off and replacement with make-up water (expedient for reducing the
electrolyte content)
− mechanical bypass flow filtration
− re-conditioning of a part flow through ion exchangers

4 Materials

Cooling water circuits are complex systems in which heat exchangers can be
exposed to diverse conditions and have to satisfy different requirements. There can
be no such thing as the ideal material that meets all these requirements. For this
reason, the choice of materials for the components of a cooling system will as a rule
boil down to a compromise. Normally there will be a some freedom of discretion that
allows a choice to be made between various materials or material systems.

In these decisions, the effects of the corrosion behaviour of the heat exchanger tube
materials in the secondary-side system may be of crucial importance (e.g. it may be
necessary to avoid the use of copper in the water/steam cycle).

Nevertheless, with the knowledge available today, it is possible to select suitable

materials from a short list of potential candidates. It is normally not necessary to
perform specific suitability tests in the cooling water.

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It is expedient and common practice to select the materials for components in

contact with the cooling water on the basis of the following criteria:
− properties of the cooling water
− suitability of materials and suitable design of components for the specific
requirements
− duty specifications to be met by the cooling system
− cost of materials and vessels

4.1 Materials and cooling water quality

Natural cooling waters contain varying amounts of salts and suspended solids and
as a rule display a neutral to slightly alkaline reaction.

With a view to the material response, it is helpful to establish a rough classification

of water qualities according to:
− total salts content
− chloride content
− suspended solids content

Ta b l e 3 shows such a classification and recommends materials for the tubes, tube
sheets and water boxes of heat exchangers (condensers) and cooling water piping
for each of the water categories. Where the table gives several options, (A) is the
preferred option, (B) and (C) may be considered as alternatives in that order (with
different reservations as regards corrosion resistance). The chloride values in
Table 3 serve by way of example only as a rough guide for the choice of materials,
which must in any case take into account the actual water chemistry and process
engineering conditions at the specific location.

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Tube material

Of the three groups of tube materials - copper alloys, stainless steels and titanium
[16], [17], [52] - use of the copper alloys for the tubing of heat exchangers in large
cooling systems is on the decline world-wide, due to the well-known risk of damage
(erosion corrosion, stress corrosion cracking, corrosion due to ammonia) [53], [54],
[55], [56], [57], [58]. Austenitic chromium/nickel steels (stainless steels) [59] and, for
brackish water and seawater cooling, titanium are today’s first choice. However, it
must be remembered that, unlike the copper alloys, these materials do not have a
bactericide effect and are thus are more susceptible to fouling by organic material
(biofouling).

Tube sheets

The choice of material for the tube sheets is largely governed by the material used
for the tubes, as otherwise compatibility problems may be encountered at the tube-
to-tube-sheet joints. There are basically four standard combinations of tube-to-tube-
sheet joints:
− any tube material and steel tube sheets coated with epoxy resin or other resin
systems,
− copper-alloy tubes and brass or bronze tube sheets
− copper-alloy or stainless steel tubes and tube sheets plated with stainless steel
− titanium tubes and titanium-plated tube sheets

Water boxes and cooling water piping

The water boxes, which are usually made of steel, are usually provided with a thin
(0.5 to 1 mm) coating or lining of the same materials as for the tube sheets to make
them suitable for use in low-salt-content cooling waters.

The material for the cooling water piping must also be matched to the water quality.
Unprotected pipes of non-alloyed steel are adequately corrosion-resistant in cooling
waters of category I (Table 3). Low-alloyed steel can even be used in waters of
category II in particularly benign conditions, i.e. if the hydrogen carbonate content
and neutral salts content of the water is in line with DIN 50930 and continuous
throughflow is present [49]. Dip-galvanized steel pipes may also be used for small-
diameter lines [60]. Otherwise, stainless steels or sturdy plastics, e.g. polypropylene,
are suitable for small-diameter lines in waters of categories II to VI; in larger-
diameter lines (as of about >200 mm), the pipes must be made of concrete or of
steel or cast iron with
− cement mortar lining
− plastic mortar lining
− plastic-enhanced cement mortar lining

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− tar/epoxy resin coating

− rubber coating [61]
or of fibreglass-reinforced plastic. If cement mortar linings are used, the cooling
water must not lie in the lime-dissolving range.

Concrete parts

The durability of concrete structures may be impaired by concrete-attacking sub-

stances in the cooling water. Lime-dissolving carbon dioxide, magnesium and
ammonium salts may dissolve the calcium compounds in the cement base or the
limestone or dolomite additives, thus weakening the microstructural cohesion of the
concrete. Sulphate ions penetrating the concrete react with certain hydratation
products of the cement to form tribasic calcium aluminate trisulphate, crystal growth
of which binds large amounts of water with associated volumetric expansion, which
produces a driving effect and destroys the microstructure of the concrete. The de-
gree of water attack can be assessed in accordance with DIN 4030 [62], [63] as a
function of the concentration of the attacking substances. The resistance of the
concrete to chemical attack largely depends on its consistency. Concrete that will be
exposed to weak or strong chemical attack according to DIN 4030 can be manu-
factured in accordance with certain rules given in DIN 1045 [64] to give it long-term
resistance. Under conditions of very heavy attack, the concrete must be protected
against direct exposure to the water, e.g. by application of a bitumen-based or plas-
tic lining.

Concrete to be exposed to attack by water with a sulphate content of more than

600 mg/l must be made using a cement with a high sulphate resistance to DIN 1164
("HS Cement") [65]. Cements with a high sulphate resistance are Portland cements
with a theoretical C3A content of not more than 3 % by weight and an Al2O3 content
of not more than 5 %wt., or blast furnace slag cements with a slag sand content of
more than 70 %wt. Concretes with hard-coal fly ash as admixture in adequate pro-
portions used in combination with non-sulphate-resistant Portland cement exhibit a
high resistance to sulphate attack.

Chlorides penetrating the concrete may cause corrosion of the reinforcement.

Penetration of chloride ions in harmful quantities can be prevented by manufacturing
a dense concrete with an adequate concrete thickness over the reinforcement and
by use of particularly suitable cements.

4.2 Materials and design

Care must be taken in the overall design of the cooling system and the structural
design of the components to ensure that the inherent resistance of the materials
selected on the basis of the cooling water quality is not impaired by overlying ef-
fects. The causes of problems in cooling systems - despite careful selection of the
material - can be traced to failure to observe certain simple rules:

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− Use of different materials in the same or successive components in the same

circuit can already increase the risk of local corrosion. For example, copper al-
loys and aluminium are mutually incompatible.
− Two materials that are otherwise corrosion-resistant in cooling water with an
electrolyte content and that are quite far apart in the real electrochemical series
must not be connected together by metallic conductors, because they would
otherwise form a single electrochemical element.
− The mechanical and structural design of the system must ensure that the cooling
water flow does not drop below certain minimum velocities, below which there is
a danger of deposition of suspended solids and formation of aeration elements.
Maintenance of certain flow velocities is also important for the operation of tube
cleaning systems and for the effectiveness of dispergents and corrosion
inhibitors; on the other hand, excessive flow velocities can cause erosion
corrosion (see Section 4.3).
− In heat exchangers with cooling water on the shell side, the necessary flow ve-
locities cannot be achieved; such heat exchangers are as a rule much less suit-
able for systems of the kind under consideration here than are heat exchangers
in which the cooling water passes through the tubes.
− The maximum allowable surface temperature for the material applies not only in
undisturbed normal operation; it must not be exceeded under any operating
conditions.
− Weld seams, even between similar metals, are as a rule less resistant than the
surrounding rolled sheet. This applies in principle also to the lengthwise seams of
automatically welded tubes. To achieve the same corrosion resistance - that of
the alloy analysis - in both the sheet and the weld, the part would as a rule have
to be cold worked and solution annealed.
− If the weld metal is a higher alloy than the sheet, the heat affected zone (HAZ)
frequently becomes a focal point of corrosion attack. Fabrication influences -
such as hot and cold working, grinding, pickling, etc. - can also have an effect on
the behaviour of the material.
− The corrosion risk can be reduced by application of a coating or cathodic pro-
tection. These are also effective against corrosion in gaps that are unavoidable
for design reasons.

4.3 Materials and mode of operation

The operating conditions to which the components of a cooling system are exposed
are also an important consideration in the choice of materials, especially for the heat
exchangers. The necessary inspection and maintenance activities must be defined
for the specific materials and site. They depend primarily on the cooling water flow
velocity, the thermal load on the tubes, and the frequency and duration of the
anticipated downtimes.

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The cooling water flow velocity is an important parameter with respect to flow-in-
duced corrosion. Determining the cooling water flow velocity by calculation alone
involves some uncertainties. The actual flow velocities should be known and, if
necessary, verified by measurement. Empirical experience shows that tubes made of
copper and copper alloys are already susceptible to erosion corrosion if the flow
velocities given in Table 4 are exceeded. This can cause an inadmissible material
depletion of > 0.05 mm/a. The attack is even stronger if the cooling water contains
erosive components such as sand (e.g. as of grain size > 0.5 mm, concentration
> 5 mg/l), or if it is super-saturated with air (two-phase flow) [66]. Under such severe
conditions, only flow velocities are allowable that lie about 20 % below the values
valid for water with a low suspended-solids content, unless mechanical or chemical
precautions - such as cathodic protection, coating, sleeving of tube inlet ends, or
dosing with ferrous sulphate - are taken to eliminate the erosion corrosion hazard.
These restrictions do not apply to austenitic chromium/nickel steels and titanium.
Unlike copper alloys, these exhibit excellent resistance to erosion corrosion even at
high flow velocities of around 5 m/s. On the other hand, the danger of corrosion
attack beneath mineral or organic deposits is particularly high in the case of
stainless steels. Because of the possibility of crevice corrosion, use of continuous-
action tube cleaning systems, usually with polishing balls, is necessary if tube mate-
rials from this group with effective sums W < 35 % [% Cr + (3.3x% Mo); German
material codes 1.4401, 1.4439] are used in connection with cooling waters with an
elevated salts or suspended solids content. This applies in particular if calcite crys-
tals can grow out of super-saturated cooling water.

Table 4. Design data for maximum cooling water flow velocities (in m/s).

Material Material No. Cooling water with low Cooling water with sand
suspended-solids or suspended solids
content content

Cu-DHP1) CW024A 1.5 -

CuZn28Sn1As1) CW706R 2.0 1.5

CuZn20Al2As1) CW702R 2.2 2.0

CuNi10Fe1Mn1) CW352H 2.4 2.0

CuNi30Fe2Mn21) CW353H 2.7 2.2

Stainless steels no upper limit

Titanium no upper limit

1)
DIN EN 12451, edition 1999-10; Copper and Copper Alloys – Seamless, round tubes for heat
exchangers

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By contrast, corrosion beneath deposits on titanium surfaces has never been ob-
served to date, so that this material is ideally suitable for heat exchangers operated
with water with a high suspended solids content. The greater susceptibility of non-
copper materials to biofouling may call for occasional or regular cleaning using
special cleaning balls, e.g. with plastic granulate or corundum coating or filled with
powdered pumice, instead of sponge-rubber balls in the tube cleaning system [58].

The temperature can influence both corrosion and deposition processes. Corrosion
processes accelerate with rising temperature; a temperature rise of 10 K nearly
doubles the corrosion rate. The crucial factor here is the actual wall temperature,
which may be widely different from the average temperature, e.g. as a result of local
differences in the thickness of deposits. Since rising temperatures also promote the
formation of crystals, the temperature influence on corrosion is particularly strong at
locations susceptible to crystal formation, Higher temperatures also promote the
growth of micro-organisms, provided there is an adequate supply of nutrients. These
processes can be controlled by use of hardness stabilisers or microbiocides and by
cleaning heat exchanger tubes to remove mineral and organic deposits, as
explained earlier.

Downtimes can have an adverse effect on the corrosion behaviour of the materials,
but there are precautions that can be taken to mitigate these effects. Heat exchang-
ers, and especially condensers, should have mineral and microbiological deposits
removed as far as possible by continuous operation of the tube cleaning system
before they are shut down for an extended period of time, and if they are to remain
filled the circulating water, which may have built up an elevated salts concentration,
should be replaced by demineralized water. Condensers are normally drained when
not in service. In this case there is a corrosion hazard from remaining water pockets
- for example in sagging tubes - in which the salts and suspended solids can
concentrate due to evaporation and eventual dry-out. Except in condensers with
titanium tubing, which do not require such precautions, condensers should be
flushed with demineralized water immediately after draining (and mechanically
cleaned if they are to remain shut down for an extended period) and dried with hot or
dry air. It is advisable to leave the water boxes open for the duration of the outage
[16], [17].

5 Monitoring by analysis

5.1 Monitoring by chemical analysis

The prime aim of monitoring cooling systems by chemical analysis is to detect in

good time any short-term changes in the coolant that could lead to trouble in opera-
tion, so as to be able to initiate counter-measures. In the long term, monitoring of the
coolant gives a picture of whether and to what extent corrosion on material surfaces
in contact with the water may be more than the unavoidable. And finally, analytical
measurements also provide an indication of whether the chemicals metering
equipment is functioning properly. The collection of analysis data for the purposes of
complying with statutory regulations and official requirements is beyond the scope of
this Guideline and thus will not be specifically dealt with in the following.

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The samples for the customary cooling water analyses are best taken at the dis-
charge side of the cooling water pumps. For a sample to be representative, the
system must have been in undisturbed continuous operation for at least two hours.
Other sampling locations may need to be chosen for special-purpose analyses. For
example, to check on the metering of chemicals, the samples must be taken down-
stream of the feed-in point; for monitoring material depletion or the condition of the
protective layer on condenser tubes, cooling water samples must be taken down-
stream of the condenser.

The constitution of the coolant is characterized by a large number of parameters.

However, their significance with respect to an assessment of the coolant and its
behaviour varies considerably. For this reason, a given parameter may have to be
measured more or less frequently, depending on its information value under the
conditions of the specific system. This must be decided on a case-by-case basis.
The following considerations and the explanations on the significance of the various
parameters in Section 5.1.1 are to be understand as an aid to making these deci-
sions.

In the case of once-through cooling, it is not common practice to perform analyses

specifically for monitoring the cooling system, if the quality of the intake water and its
seasonal fluctuations are sufficiently known. Usually, the supplying waterbody will be
analysed regularly anyway, for other reasons; its constitution must also be known if
the water is pre-treated in a treatment plant. The data material available from such
analyses generally supplies all the information required for judging the conditions in
a once-through cooling system. Exceptions are the determination of the copper
concentration upstream and downstream of the condenser and possibly, in systems
operating with seawater or brackish water, measurement of the sulphides from
fouling processes. If microbiocides are used, this likewise requires regular
monitoring analyses to check for compliance with the desired service concentrations.

In the case of open-circuit recirculation cooling systems, the situation is different. In

these systems, some basic parameters should be continuously or periodically
measured in the circulating water (Ta b l e 5 ), including those that have a bearing on
discharging the blowdown. There are also quite a number of other parameters which
it is sufficient to monitor at longer intervals, depending on the specific system and
site. The cooling tower make-up water must also be analysed in parallel with the
circulating water in order to be able to establish a correlation and to draw conclu-
sions as to the rate of concentration factor due to evaporation losses.

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Table 5. Minimum scope of analyses for monitoring the circulating water in open-circuit
recirculation cooling systems.

Recommended frequency of
Basic parameters
measurement

Temperatures
(upstream and downstream of loads) cont.

Conductivity (direct measurement) cont./(d)

pH value cont./(d)

KS 4.3 / KS 8.2 d/(w)

Ca + Mg w/(req.)

- 2-
Further parameters, such as Cl , SO4 , P and N compounds, Cu, Fe, Na (K), COD
(DOC), undissolved substances, colony count, concentration of dosed chemicals
should be monitored according to criteria defined for the specific system and site.

cont. ⇒ continuous recording

d ⇒ daily
w ⇒ weekly
req. ⇒ as required

Monitoring of closed-circuit recirculation cooling systems using demineralized make-

up water can be limited to just a few parameters, especially since there is no
evaporation and concentration factor. The monitoring programme suggested in
Ta b l e 6 should be adequate for assessing the ongoing processes in such systems.

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Table 6. Minimum scope of analyses for monitoring the circulating water in closed-circuit
recirculation cooling systems.

Recommended frequency of
Basic parameters
measurement

Conductivity


as auxiliary para-
direct measurement req.
meters instead of
measurement downstream of strongly req.
pH measurement
acidic sampling cation exchanger

Oxygen req.

Dosed chemicals req.

TOC (hydrocarbons) req.

Fe / Cu req.

req. ⇒ as required

5.1.1 Significance of cooling water analysis parameters

Temperature

Indispensable correction parameter for precise determination of electrical conduc-

tivity, pH value, oxygen saturation and lime/carbon dioxide equilibrium.

Electrical conductivity

Nonspecific global parameter for the electrolyte content in the cooling water.

The electrical conductivity can be continuously recorded by relatively simple means

and is first and foremost a measure of the overall salts content. Provided that the ion
concentration ratio remains roughly constant and subject to suitable calibration, the
electrical conductivity measurement also gives an indication of individual dominant
components, e.g. chlorides in brackish water.

In open-circuit recirculation cooling systems, the concentration factor can be

determined with sufficient accuracy from the ratio of the conductivities of the circu-
lating water and make-up water, In closed-circuit recirculation cooling systems using
demineralized water or condensate as make-up water and soda lye or ammonia as
conditioning agents,

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− the directly measured conductivity serves, by virtue of the correlation between

the alkalinisation agent concentration, the conductivity and the pH value of the
coolant, as an auxiliary parameter for determining the pH value and metering the
alkalinisation agent,
− the electrical conductivity measurement downstream of a strongly acidic
sampling cation exchanger serves to detect ingress of salts from outside the
system.

pH value

A measure of the hydrogen ion and hydroxide ion concentration; an important pa-
rameter for measuring corrosion attack.

In open-circuit recirculation cooling systems, the circulating water is usually buffered.

Short-term, pronounced changes in the pH value can occur only under adverse
circumstances, for example by aspiration of acid gases from the environment or due
to microbiological activity. In closed-circuit recirculation cooling systems operated
with practically oxygen-free demineralized water (condensate) and isolated from the
atmosphere, the corrosion hazard to metallic materials is low at pH values > 7.

Acid capacities KS 4.3 / KS 8.2

Nonspecific parameters that can be regarded as a measure of the buffer capacity of

the water.

In open-circuit recirculation cooling systems it is of interest to know the acid capaci-

ties if the cooling tower make-up water is decarbonated by means of lime, doping
with acid or ion exchange. The hydrogen carbonate concentration can be derived
with reasonable accuracy from the values for KS 4.3 / KS 8.2. A reduction in the hydro-
gen carbonate concentration in the circulating water if there is little change in the
concentration factor and a constant make-up water quality is an indication of the
precipitation of calcium carbonate, provided that external influences, such as the
entrainment of acid gases with the cooling tower air, can be ruled out.

In closed-circuit recirculation cooling systems with demineralized water as make-up

water, the acid capacity is of no importance.

Hardness

A measure of the overall concentration of alkaline earth ions, in most waters identical
with the calcium and magnesium ion content.

In open-circuit recirculation cooling systems, a hardness deficit - determined with

allowance for concentration factor - between the cooling tower make-up water and
the circulating water is an indication of the precipitation of calcium carbonate in the
system. Slight hardness losses may be due to the build-up and up-keep of protective
layers on material surfaces.

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In closed-circuit recirculation cooling systems, hardness measurement is less im-

portant as a means of leakage monitoring than is conductivity measurement.

Chloride

A significant parameter for the corrosion behaviour of metallic materials; a local

build-up can trigger corrosion.

In open-circuit recirculation cooling systems, the concentration factor can be reliably

determined from the chloride contents of the make-up water and circulating water, as
the chloride concentrations otherwise do not change.

Sulphate

A significant parameter for the corrosion behaviour of concrete materials [14] which,
for this reason, must not exceed certain concentrations.

This must be borne in mind if sulphuric acid is used to decarbonate the water.

Phosphor compounds

Phosphor compounds occur in various species, such as orthophosphate, polyphos-

phate and organic phosphor derivatives (mainly phosphonates).

In open-circuit recirculation cooling systems, the phosphor concentration must be

monitored - also with regard to complying with discharge quality requirements - if the
make-up water already contains phosphates or hardness stabilisers on a phosphor
basis are used for conditioning the circulating water.

Nitrogen compounds

A generic term for various species, such as ammonia, nitrate, nitrite and organic
nitrogen compounds; elevated ammonia, nitrate and nitrite contents in the cooling
water are an indication of microbiological processes as a result of which corrosion
can occur.

Copper

An indication of ongoing corrosion and for the behaviour of the protective layers on
heat exchanger tubing made of copper-based alloys.

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Total iron

An indication of ongoing corrosion in iron-based materials and a parameter for

checking compliance with the desired service concentration if ferrous sulphate is
added to the water.

Sodium, potassium

Parameters that are of no importance to operation of the cooling system but knowl-
edge of which makes it possible to close the ion balance and to demonstrate the
plausibility of a cooling water analysis.

Oxygen

Certain standards are recommended for closed-circuit recirculation cooling systems,

and compliance should be monitored.

COD (TOC)

Nonspecific global parameter for the chemical oxygen demand of the cooling water.

In open-circuit recirculation cooling systems, the COD (or the DOC/TOC content)
makes it possible to draw conclusions as to the presence of (oxidisible) organic
contents in the cooling water.

Undissolved substances

Global parameter for contaminants in a cooling system.

In an open-circuit recirculation cooling system, undissolved anorganic substances

give an indication of problems with the build-up and/or up-keep of protective layers
and of the presence of possibly abrasive material (erosion, erosion corrosion). Un-
dissolved organic substances may be a sign of intensified microbiological activity.
More detailed information can be obtained only by examining the composition of the
undissolved substances or at least determining the organic loss on ignition.
Monitoring the colony count in the circulating water can also be useful in this con-
nection.

The high adsorption of chlorine and chlorine bleach into the undissolved substances
may cause chlorine depletion if these substances are used for biocide treatment.

Chemical agents

The service concentration of conditioning agents should be controlled via the input
flow. It may, however, also be necessary to measure the content of the effective
agents in the circulating water directly. Direct or indirect measurement of the input
chemicals may make it possible to reduce the amount of chemicals used.

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5.2 Microbiological analysis

To guard against trouble in service, it may be necessary to examine the cooling

water for microbiological activity. At the same time, microbiological analysis provides
data on the potential health hazard emanating from cooling systems [48].

The nature and frequency of microbiological activities depends on

− the type of cooling (once-through cooling, recirculation cooling, etc.)
− the type of cooling water (seawater, brackish water, etc.)
− the materials used and the surface condition of the materials in the cooling sys-
tem
− the nutrient content of the cooling water
− the water temperature
− exposure to sunlight
− the flow conditions in the cooling system
− tube clogging

If a tube cleaning system is installed in the cooling system, attention must be paid to
ensuring that it is fully operational in order to avoid biological deposits in the heat
exchanger tubes (impaired heat transfer, higher corrosion rate). If necessary, tube
cleaning balls with abrasive coatings (corundum, granulate) must be used in times of
high biological activity to remove deposits on the tube walls.

5.2.1 Investigations

The frequency of investigations will depend on the microbiological activity and the
type of cooling water.

Use of test heat exchangers in cooling systems gives an overview of the biofouling
hazard. However, these measurements provide reliable results only over long
periods.

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Parameter Method

Colony count The number of reproducible germs (colony-forming

units) per unit volume is determined in accordance with
DIN 38411-5 (K5).
4
A reproducible germ count of < 10 /ml is an indication of
trouble-free operation in terms of the biological burden.

ATP ATP is present in living micro-organisms and is measured

(Adenosine photometrically after dosing with enzymes (luciferase)
5’triphosphate) (instant test)

Light-emitting bacte- Determination of the biocide activity in the cooling water in

ria test accordance with DIN 38412-34 (L34).

5.3 Monitoring for corrosion

The susceptibility of materials in cooling systems depends on the water quality

(chemical substances present, solids content) and on the materials used.

5.3.1 Investigations

Material specimens can be integrated into the cooling system for assessment of the
corrosion potential.

Two systems have a proven service record:

− Test heat exchangers
Specimen tubes made of the materials used in the cooling system are inserted in
a test heat exchanger installed in a bypass flow of the actual cooling water. The
advantages of this system are that it covers not only the specimen material as
such but also the fabrication influences and that defined temperature gradients
can be simulated.
− Coupon test
Coupon holders, into which material specimens (coupons) can be inserted, are
installed in a bypass, preferably downstream of the condenser (ASTM G1 - 81).
As a rule, external heating is not possible.

The corrosion rate is determined gravimetrically by acid-stripping the corrosion layer.

These tests are long-term tests and do not provide instantaneous values. Use of
electrochemical on-line monitoring systems supplies instantaneous readings for

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scaling, fouling and biofouling. These results indicate trends and have to be nor-
malised by long-term testing.

A further option is to use sophisticated laboratory corrosion apparatus for experi-

mental operation with cooling water specimens. These apparatus are particularly
helpful in the selection of materials and, where inhibitors have to be used, in
choosing between different products.

Investigating the causes of microbiologically-induced corrosion requires specific

microbiological testing [67].

6 References
[1] Behrsing, V., Grimm, W., and Wittrowsky, G.: Investigation on the Treatment of Lime-
decarbonized Cooling Tower Make-up Water for Use as Secondary Cooling Water.
VGB PowerTech 68 (1985) No. 2, pp 147-150.
[2] Martin, P.: Some Thoughts on Co-ordinating the Operating Characteristics of Turbine
and Condensator. VGB PowerTech 68 (1988), No. 6, pp. 540-545.
[3] DIN 1947, edition 1989-05
Thermal performance acceptance testing of water cooling towers (VDI Code of
practise).
[4] Buss, E., and Engel. L.: Aspekte moderner Kühlwasserpflege. Erdöl und Kohle -
Erdgas - Petrochemie vereinigt mit Brennstoffchemie 30 (1977), No. 7, pp. 322-328.
[5] Trage, B., and Hintzen, F.J.: Design and Construction of Plants with Indirect Dry
Cooling Systems. VGB PowerTech 69 (1989), No. 2, pp. 164-170
[6] Ham, A.J.: The Conservation of Water as a Power Plant Resource. VGB PowerTech 69
(1989), No. 1, pp. 15-21
[7] DIN EN 45510-6-3, edition: 1998-06
Guide for procurement of power station equipment - Part 6-3:
Turbine auxiliaries; condensator plant; German version of EN 45510-6-3: 1998.
[8] Alt, W., and Mäule, R.: Hybrid Cooling Towers in an Economic Comparison with Wet
and Dry Cooling Towers. VGB PowerTech 67 (1987), No. 8, pp. 689-694.
[9] Enger, R., Blanck, D., and Schwickert, M.: Hybridkühltürme als Teil einer Kühl-
wasserversorgung. VGB Conference "Kühltürme 1991", (TB 602) Lecture 3, parts 1-3.
[10] Münch, S., and Fichtner, H.: The Hybrid Cooling Tower for the 2x60-MW West Co-
generation Plant of Stadtwerke Frankfurt am Main. VGB PowerTech 71 (1991), No. 6,
pp. 501-505.
[11] Cossmann, R., and Vodicka, V.: Hybridkühltürm für einen 1300 MW-Block.
Brennst. - Wärme - Kraft 36 (1984), No. 7-8, pp. 310-313.
[12] Kühlwasser, 4th revised and extended edition, 1994, by H.-D. Held, revised by H. G.
Schnell. Vulkan-Verlag Dr. W. Classen, Essen
[13] Effertz, P.-H., and Fichte, W.: Kühlwasserseitiger Schutz von Kondensator- and Kühler-
berohrung durch Eisensulfatdosierung. Der Maschinenschaden 49 (1976), No. 4, pp.
163-172.
[14] Effertz, P.-H., and Fichte, W.: Iron Sulphate Dosing in Cooling Systems; Fundamentals
and Application. VGB PowerTech 57 (1977), No. 2, pp. 116-120.
[15] Stubbe, J., and Briquet, J.: Assessment of FeSO4 Dosing of a Heat Exchanger. VGB
PowerTech 69 (1989), No. 7, pp. 631-634.

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[16] VGB Guideline "Tubes for Condensers and Other Heat Exchangers (Part A Copper
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inside of tubes, tanks and apparatus; evaluation of the corrosion likelihood of unalloyed
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(TB 433), lecture R 5, size 12 pages.

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Corrosion of metals; corrosion of metallic materials under corrosion load by water
inside of tubes, tanks and apparatus; evaluation of the corrosion likelihood of hot dip
iron materials.
[61] Freier, R.K., Herms, R., and Kallenbach, R.: Experience with Coatings in Plants in
Contact with Water. VGB PowerTech 56 (1976), No. 2, pp. 98-102.
[62] DIN 4030-1, edition: 1991-06
Assessment of water, soil and gases for their aggressiveness to concrete; principles
and limiting values.
[63] DIN 4030-2, edition: 1991-06
Assessment of water, soil and gases for their aggressiveness to concrete; collection
and examination of water and soil samples.
[64] DIN 1045, edition: 1988-07
Structural use of concrete; design and construction.
[65] DIN 1164-1, edition: 1994-10
Cement - Part 1: Composition, specifications.
[66] Effertz, P.-H., and Forchhammer, P.: Parameterstudie zum Erosions-Korrosions-
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(1994), pp. 5-9.

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