Paper accepted for presentation at 2003 IEEE Bologna Power Tech Conference, June 23th-26th, Bologna, Italy

Technology for the treatment of the used waters

resulting from the softening process
A. Stanca, P. Budulan, A. Serbanescu, A. Raducanu, L. Amza, V. Brinzoi and G. Stanca
Abstract--The waste waters from the Romanian power plants
mainly result from the water treatment stations and partially
from the continuous blow down from steam boilers, from the
liquid ash removal/slag removal, the hydro technical circuits, the
boiler chemical cleaning, air re-heaters, the blow down from the
cooling systems, the gravitational separators of oil.
In agreement with the fuel used (power plants with or without
ash dump), the power plant location and the sewage system
configuration, the wastewater is discharged in: the slag and ash
dump, the rivers, the lakes and directly to the town sewage
system.
The discharge requirements impose the treatment of the
wastewaters resulting from the power station.
This paper presents a modern technology for the treatment of
the wastewater resulting from the softening process.
Index termschemistry, chemicals analysis, corrosion,
corrosion testing, iron compounds, water heating, water pollution

In most of the cases, the power plants located in towns also

supply the heat carrier for the district heating networks. From
the water softening technological process great amounts of
wastewater with a high salinity are obtained. This water is
directly discharged into the sewage system of the town.
The high salinity of these waters, as a result of the calcium,
magnesium and natrium chlorides presence in the water,
inhibits the biological treatment process in the town water
treatment stations.
At present the only way to diminish wastewater salinity, to
be discharged within the allowable limits is dilution, requires
great volumes of water. At the same time wastewater
homogenization basins (tanks) are also necessary to eliminate
peak concentrations [5].
There are two variants for the treatment of highly salted used
waters, namely:
A. Stanca is Senior Researcher with National Institute of Energy
Research and Development, Bucharest, Romania
P. Budulan is PhD Engineer with National Institute of Energy Research
and Development, Bucharest, Romania
A. Serbanescu is Senior Researcher with National Institute of Energy
Researcher and Development, Bucharest, Romania
A. Raducanu is Senior Researcher with National Institute of Energy
Research and Development, Bucharest, Romania
L. Amza is Researcher with National Institute of Energy Research and
Development, Bucharest, Romania
V. Branzoi is Professor PhD with Polytechnic University of Bucharest,
Romania
G. Stanca is Senior Designer with Institute of Mechanical Research,
Bucharest, Romania

0-7803-7967-5/03/$17.00 2003 IEEE

- The chemical treatments to remove total hardness of

water and treated water re-utilization as a regeneration
solution;
- Salt removal from wastewater by making it passes
through reverse-osmosis filters and treated water
reutilization as technological process water.
These treatment variants are used both for the
environmental problems solving, by considerably diminishing
the discharged wastewater amounts to the indices allowed by
legislation and the diminishing of the costs of the
technological process water and of the regeneration reagents
of the Na-cationic filters.
I. LABORATORY TESTS
Chemical treatment tests of the wastewater resulting from
the Na-cationic filters have been carried out in the lab in order
to obtain treated water that can be reutilized for subsequent
regenerations [3].
The lab tests were performed in order to attain two goals:
- establishment of the optimum conditions for calcium and
magnesium hardness precipitation and for correcting the
sodium chloride concentration in the resulting waters, to
the concentration necessary for the Na-cationic filters
regeneration;
- verification of the treated wastewater influence on the
process of their reutilization for the Na-cationic filters
regeneration.
The reactive agents used for settling were sodium carbonate
and sodium hydroxide.
The parameters envisaged for the optimum precipitation
condition of calcium and magnesium hardness were:
- the utilized precipitation reactive agents;
- the dose of reactive agents operating;
- working temperature;
- settling down time;
The tests have been carried out under mechanical stirring
conditions for 15 min (60 rotations/min). Then the samples
were left to settle for an hour. After this time, analyses of the
supernatant water were performed.
The technology for the treatment of the wastewater
resulting from Na-cationic filter regeneration was developed
on the basis of the results obtained during the testing of the
water samples taken from the thermal power plants.

II.THE PRINCIPLE OF THE TECHNOLOGY UTILISED TO

TREAT THE USED WATER RESULTING FROM THE
SOFTENING PROCESS
The technology aims at eliminating calcium and
magnesium hardness by a chemical precipitation process, the
restoring of the concentration of sodium chloride as a
regeneration reactive agent, and reutilization of the solution
for a new regeneration [1].
The basic reactions that take place are the following:
CaCl2 + Na2CO3 CaCO3 + 2NaCl
MgCl2 + 2NaOH Mg(OH)2 + 2NaCl
The wastewaters resulting from the backwash, regeneration
reagents dosing and slow rinse operations (about 70 m3 since
the beginning of the slow rinse operation) are collected in a
treatment reactor and homogenized.
Total hardness, calcium hardness and magnesium hardness
are determined.
In the reactor the used water is warmed up to 30-35 0C by
steam intake.
Determined amounts of sodium carbonate and sodium
hydroxide are dosed. In the reactor the solution is mixed for 15
minutes, then the stirring and the steam are stopped and it is
left to set for 60 minutes for settling.
The efficiency of precipitation is checked by total hardness
analyses.
After the sludge settles, it is discharged into the existing
sludge tanks. The clear supernatant is discharged through
pumping into a tank for pH correction. The automatic dosing
of hydrochloric acid performs the pH correction up to 8,0-8,4.
After the pH correction, the treated used water is discharged
into a buffer tank, which is used for the following purposes:
- sodium chloride dissolution in the salt cell and
preparation of the concentrated salt solution (up to 2025%);
- backwashing of the Na-cationic filters;
- dilution water for the sodium chloride (up to 10%)
preparation;
- counter-flow water during the dosing of regenerating
agent.
The schematic diagram of the wastewater installation
resulting from the softening process is presented in figure
III.WATER CONDITIONING FOR CORROSION
PREVENTION
Due to the expansion of the district heating system, the
enough waters treatment capacity does not secure conditions
for optional functioning.
The experience in exploitation, revealed the presence in the
district heating systems of serious corrosion phenomenon the
lead to: wholes in the pipes of the heat changers and in the
thermal transport pipes; significant losses of thermal energy,
high exploitation and surveillance expenses supported by both
industrial al private users [6].
Today world wide everybody uses complementary methods
of corrosion reduction: the chemical conditioning of the water
used in district heating, which contains complex correction

treatments of water quality with the purpose of fighting

against corrosion and deposits.
In the national research program, our specialists developed
a technology in water conditioning from the district heating
systems at the same level us to the international technologies
are, that guarantees working without any problems.
The introduction of this technology in industrial equipments
will lead to the reduction of hot water and steam, expenses for
resources therefore to reduction of the thermal energy price.
This work presents the theory and researches made for
creating and developing a technology in conditioning of the
water from the district heating systems, for fighting against the
advanced corrosion process from the district heating systems.
The research has an effect upon the price of the thermal
energy price by the consumers.
This work presents the theory and researches made for
creating a water treatment technology there have been made
further laboratory experiments to prevent corrosion
equipments.
The evaluation of the conditioning efficiency of substances
was through gravimeter tests in high corrosion environments
and potentiometer determinations [4], [2].
The laboratory experiments were done in the following
conditions:
- the degassed and softened water, with the oxygen level of
0,2-0,3 mg/l, over the international limits, according to
the situation inside the installation.
- this softened water with oxygen levels at solubility levels.
This is the situation in many stations where the
degassed capacity was not enough so the process was
dropped [8].
The creation of this technology consists of the use of
certain compounds that better and complete the initial
treatment of the supply and additional water occurred in
the water treating installations.
The purpose of water conditioning consists of:
- the inhibition of the metallic surfaces corrosion process
- the correction of water alkalinity
- setting the hardness
- the dispersion of organic and inorganic depositions
Modern technologies for this process use substances based
on polyelectrolytes, trisodic phosphate, sodium sulfite that
doesnt allow for the reaction between the oxygen in the water
and the iron in the steal pipes and in the district heating
circuits equipment to take place.
Whatever the corrosion inhibitor type is, to be efficient, it
has to have the following properties:
stability, resistance to eventual degradation processes
(working temperature)
fast activity after being placed in a rough environment
the insurance of the inhibitor effect in the working
conditions of the protected installations, temperature,
pressure;
it must not take part in the growth of physical or chemical
processes
the big capacity of protection against low concentrations
for not polluting the environment and for economical
justification

IV.EXPERIMENTS FOR INHIBITORS EFFICIENCY

EVALUATION
For the evaluation tests upon the inhibiting action, the
ICEMENERG research team thought and realized the
experimental laboratory installation. In the creation of the
experimental scheme the following facts were considered
important:
the achievement of the dynamic conditions of water
stirring
heating the substance up to 70-80C, temperature when
the corrosion process is accelerated.
assuring the open circuit conditions, with air access in the
experimental installation, so that the oxygen sets at the
solubility limit.
The accelerated laboratory experiments were made in tubes
made from the same steal as in the industrial installations, with
parallelepiped shape with the dimensions 50 X 20 X 2 mm.
The water used to prepare the inhibitor substances for the
tests was synthetic prepared in the laboratory, according to the
testing processes of inhibitors specific for district heating
circuits. In the test recipients the substances were inserted.
The accelerated tests were made for the following time
lengths: 24 h, 48 h, and 72 h.
Sets of 4 experimental results we measured at the same
time, the experimental conditions being the same for all sets of
tests. The inhibitors efficiency was evaluated in relation with
the witness test, in which was inserted synthetic water without
any inhibitor, by evaluating:
the corrosion speed of the steal made tubes in
experimental environments.
the iron concentration in the experimental substances
In every testing period there were analyzed both the test
tubes and the remaining substances from the test tubes. There
were determinate the following chemical parameters:
conductivity, pH, p & m, alkalinity. The results were inserted
in the table and will be graphically presented.
The working methods are according to the ISO 9226/1995
laws.
According to this domains theoretical data, the maxim
allowed speed in the work environments, for the products to
assure the corrosion inhibition must be 0.1 g / m2h.
During the experimentation, after passing the experimental
time, the substances in which the corrosion inhibitions were
dozed were analyzed.
From the study of these results was noticed the presence of
iron in the substance is directly related to the corrosion speeds
and to the protection efficiency [7].
The results of the experiments were graphically
represented, in the drawings.

Considering the experimental tests and results obtained,

there could be evaluated water conditioning technologies for 2
different situations:
technologies of chemical conditioning of the water from
the closed district heating systems, were thermal
degasification occurs and the corrosion inhibitors assure
the basic metal protection where the oxygen exceeds the
limit 0.2-0.3mg / l. This is the case in almost all the
thermal power plants. In this case, the inhibitor role is to
block the reaction between the remaining oxygen from the
degassed water and the metal surface of the heat changer
or of the transport pipe:
water conditioning technologies in the systems where the
thermal degasification of the water does not occur. This is
the case of local thermal stations but not of the high
capacity plants. In this case, the district-heating network
grew but there werent built other thermal degasification
systems.

120

Ferrofos 8579 3g/l

Ferrolix 332 5g/l

100
conc. Fe (mg/l)

the protection layer must be leak-proof against

environmental factors and to insure a long lasting
protection.
not to allow secondary processes of metal softening.
Because of possible water infiltration from primary to
secondary system and water with conditioning products, we
will consider how these affect the population.

Hydro-x 5ml/l

80

Hydro-x 10ml/l

60

Hydro-x 20ml/l
Ferrofos 8579 1g/l

40

Ferrolix 332 1g/l

20

Ferrolix 332 3g/l

Blank

0
24

48

72

time (hours)

V.CONCLUSIONS
The laboratory tests established:
- the optimum conditions for the calcium and magnesium
hardness precipitation (reactive agents and their doses,
operating temperature, settling time);
- the optimum physical-chemical indices of the treated
wastewater (pH, "p" alkalinity, total hardness and
carbonic hardness), necessary for the re-utilization of the
treated water for the subsequent regenerations of the Nacationic filters. The insurance of these indices prevents
the diminishing of the useful capacities of ionic
exchanges, under the conditions of the treated water
reutilization as a regenerative solution;
- the technology for the wastewater treatment in order to
reuse it as a regenerative agent.
The advantages of applying this technology are the
following:
- full reutilization of the treated wastewater in the process
of backwashing and as a regeneration solution in the Nacationic filters;
- a great diminishing in the volume of the waste water
discharged from a of power plant that produces softened
water for the district heating networks;
- environmental pollution diminishing through the
reduction of the discharged waters with a high salt
content;
- diminishing of corrosion in the wastewater transport
pipes, by reducing the waste waters chloride content;

diminishing of the power plant costs by recovering the

regenerative agents of the Na-cationic filters;
- reducing the power plant costs by diminishing the
technological process water consumption and the costs for
the volume and quality of the discharged water.
Checking on the corrosion inhibitors efficiency took place
in 2 ways:
- tests with thermal degassed cation exchange softened
water.
- tests with cation-exchange in softened water, with oxygen
at solubility levels
The estimation of the corrosion inhibitor efficiency was
determined through more processes:
- gravimeter tests
- potentiometric tests
- iron test in the experimental substances.
Analyzing the operation sheet of the products, their
chemical composition, the configuration of the heating
systems (closed systems, systems with possibilities of
infiltration in the secondary heating system), the concentration
of the reacting substance resulted, we propose the next ways
of treatment:
- for the closed systems of heating, with great possibilities
of heating, where there is the risk of infiltration in the
secondary systems and the water is not degassed, it is
recommended to use the product Hydro-x in 5 ml / l
concentration.
- for the district heating systems with low capacities,
closed, where there is no risk of water polluting in the
secondary systems (new power plants with stainless
exchangers) and where the water is not degassed it is
recommended to use the product Ferrofos with a 3 g / l
concentration.
- for the heating systems where the water is not enough
degassed and where there is the risk of water polluting in
the secondary system it is recommended to use the
product Hydro-x in a 10 ml / l concentration
- for the low capacities closed heating systems, where there
is the risk of water polluting in the secondary systems
(new power plants with stainless exchangers) and where
the water is degassed it is recommended to use the
products Optisperse in a 33 mg / l concentration,
respectively RGCC 100 in a 2,73 mg / l concentration.
- using the products with well results only for no risk of
water polluting systems is due to the fact that those ones,
by their composition, can affect peoples health
- the only product that presents no risk on peoples health
(according to the operation sheet and the sanitary
attached) is Hydro-x.

VI.REFERENCES
[1]
[2]

[3]
[4]

[5]

[6]

[7]

[8]

Periodicals:
N.PESCHEN - Industrial waste water from purification with lime
products. Abwassertechnick 5: 24 - 27, 1986
C.K.Walker s.a.- Corrosion - Monitoring Techniques and Applications Materials Performance, May, 1989
Books:
HANS-GNTER HEITMANN - Handbook of Power Plant Chemistry.
Ed.1993;
Metals Handbook -Ninth Edition - Volume 13 - Corrosion - ASM
International Committee- 1989
Technical Reports:
UNIPEDE Report apr. 1997 regarding wastewater treatment in power
plants from European Union
Paper from Conference Proceedings (Published)
A.Stanca-Aspects on the Behavior of District Heating Circuits under
Variation of Chemical Duty and Operations Conditions. Future
Development Trends -International Conference on Conventional and
Nuclear District Heating, Lausanne, Switzerland, march 18-21, 1991,
vol Conference, page 95
A.Stanca, A.Raducanu, A.Serbanescu, A.Bolma, L.Amza, G.StancaInternational 4E Symposium, Struga Macedonia, 3-4 oct.2002
Optimisation of the Thermal Energy Generation and Transport Network
using Water Conditioning in District Heating for Corrosion Prevention
Vol. Symposium, page 293
Standards
VGB Guideline for Boiler Feed water, Boiler Water and Steam of Steam
Generator - VGB - R 450 Le 1995

VII.BIOGRAPHY
Angela Stanca was born in Iasi, Romania, on December 27, 1955. She graduated
from Polytechnic University of Bucharest Faculty of Chemistry
She is a senior researcher at the National Institute for Energy Research and
Development and a PhD Student in Chemistry at Polytechnic University of
Bucharest.
During her activity she was a managed projects in the following areas:
- power plant water treatment;
- power plant chemistry, corrosion and scale in water, inhibitors;
- drinking, technological and waste water treatment, monitoring
of water quality
- chemical cleaning technologies for the boilers, heating

fly ash waste reuse

assistance for different problems regarding environmental, water
treatment and corrosion.