13.
NEUTRALIZATION – REMINERALIZATION
Treatments designed to correct the pH
are often referred to as neutralization
treatments and consist in bringing the pH
of water into line with a defined value.
They may be employed in the following
areas:
- the neutralization of various effluents
with a pH often close to neutral before
being discharged into the environment:
industrial effluents that are acidic or
alkaline, acidic waters from mine
drainage, etc.,
- the correction of the pH before a further
biological or physical-chemical treatment
stage (adjustment of the flocculation pH,
for example),
- the correction of the carbonate balance
in order to protect the supply pipelines
from corrosion or scale formation.
This last point in particular will be
expanded upon because it constitutes an
important stage in the treatment of
drinking water and industrial waters.
In fact, water with calcium bicarbonate
corrective treatments:
- aeration,
capable of initiating the formation of a
natural protective film known as Till- 261
man's film (see page 425). The conditions
surrounding the formation of this film
may involve all or part of the following
- neutralization of carbonic acidity until
the saturation pH is achieved for
aggressive waters or, on the contrary,
acidification of scale-forming waters,
- remineralization of waters short of
calcium bicarbonate.
In the absence of conditions necessary
for the formation of the protective
carbonate film, the protection of the
supply network may also be insured:
- against corrosion by a film-forming
treatment based on corrosion inhibitors,
- against scale formation, notably that due
to salts other than calcium carbonate, by a
chemical conditioning of water (involving
the formation of soluble compounds
which is adequately oxygenated pounds)
apart from methods of precipand in
carbonate balance is, when cold, nation,
ion exchange or demineralization.
 Chap. 3: Basic physical-chemical process in water treatment
13.1.
THE CARBONATE BALANCE
Natural water is not pure and contains
various dissolved chemical elements, the most
common of which is calcium bicarbonate (or
hydrogen carbonate).
The practical balance of this salt with
carbon dioxide is governed by rather complex
laws, and shifting it can provoke chemical
reactions causing the dissolution of calcium
carbonate (or aggressiviry), or the
precipitation of calcium carbonate (or scale
formation) which can add to simple
electrochemical corrosion reactions particular
to the metals.
13.1.1. General study of balance Concepts of
aggressivity and corrosivity
All studies of carbonate balance are based
on the following equations:
- the equality of positive and negative
electrical charges:
ions and carbonic acid are fundamental
factors of the carbonate balance. The N and
P ions which essentially involve the ionic
strength of the solution are secondary factors
with regard to the balance and are defined by
Legrand and Poirier ascharacteristic
elements
Temperature is also an important factor
influencing the value of dissociation
constants.
The term E depends on the ionic strength
~1 of the solution according to the equation:
and the ionic strength ~t expressed in
moles by litre is defined by the relation:
Ci and zi are respectively the
concentrations in moles per kg and the
valences of the various ions present in the
solution.
Using the preceding equations the
saturation pH may be calculated by
substituting in equation (4) of water at
equilibrium the value of C03 2- by one
obtained from equation
Thus, it is necessary that pH = pH, for the
water to be unaffected by calcium carbonate
scale; consequently, it will not attack the
walls of the cisterns, the tanks or the
pipelines. The concentration of CO2 which
corresponds exactly to pH, is known as
equilibrium CO2 .
 13. Neutralization - Remineralization
The pHs corresponds to the saturation pH
of the water under consideration for identical
values of bicabonates and calcium, that is,
saturation pH achieved by the addition or
escape of carbon dioxide.
If the pH is lower than the pHs, the water
has a tendency to dissolve the lime and attack
the cement, the concrete, etc. It also renders
impossible the formation of a protective
carbonate film on the metal pipelines because
of the redissolution of CaCO3 which
progresses at the same rate as it is
precipitated. Such a water is known as
aggressive; the fact that the pH level is too
low is due to an excess of carbon dioxide,
which is referred to as aggressive CO2 . The
total concentration of dissolved CO2 in this
case is therefore equal to the some of the
equilibrium CO2 + the aggressive CO2 . It is
this excess of CO2 that must be removed or
transformed during the treatments known as
neutralization treatments.
If the pH is higher than the pHs, the water
has a tendency to precipitate limestone in
contact with CaCO3 nuclei, and the water is
referred to as scale-forming; in this case, its
free CO2 concentration is lower than the
theoretical value of equilibrium CO2 . To
combat scale formation, either the pH must be
lowered to bring it in line with the
equilibrium value or a softening or carbonate
removal treatment must be carried out (see
page 146).
Thus, regulating the saturation pH is a
necessary condition although it is not
sufficient to avoid corrosion in some cases.
13.1.2. Techniques for calculating
aggressivity – Diagrams
In practice it is interesting to study the
evolution of the six constituents H+, OH-,
CO3 2-, HCO3 -, Ca 2+ and H2 CO3 and to show
this by means of graphs. Any two basic
constituents are taken as coordinates, and the
graph enabling the curves representing the
various elements linked to the carbonate
balance of water to be simply constructed is
selected on the basis of fundamental
equations of equilibrium.
Using different variables a large number of
diagrams may be drawn up from which the
most commonly used may be referred to.
13.1.2.1. Langelier's method
Using the general equation (6) to calculate the
pHs, Langelier devised a calculation graph
incorporating alkalinity and calcium
expressed as mg.l-1 CaCO3 , the total salinity
(dry residue in mg.l-1 ) which influences,
through the ionic strength, the value of the
apparent coefficients involved in the
dissociation of balances, and temperature.
The pHs may be calculated from the
diagram (see Figure 122) by the equation:
pHs = C + pCa = pAlk with C = pK'2 - pK'S
Langelier also established index SI, the
saturation index, equal to the difference
between the measured pH in a considered
water and its calculated pHs:
SI=pH-pHs
If pH G pHs, SI is negative and the water
is aggressive.
If pH > pHs, SI is positive and the water is
scale forming.
This resolution takes into account a salinity
of up to about 3 g.l-1 and temper
 Chap. 3: Basic physical-chemical process in water treatment
ature, but does not permit amounts of
neutralization reagents to be calculated.
In the case of brackish water, and especially
sea water, the correction proposed by Stiff and
Davis in the pHs calculation (see Figure 123)
is employed.
pHs = K + pCa + pAlk where K = pK'z - pK's
13.1.2.2. Hallopeau and Dubin method
These authors have devised a graphic method
of determining the aggressive action of water
on limestone and of calculating the amounts of
neutralizing reagents, by expressing the
saturation pH in terms of the logarithms of
alkalinity (measured by the M alk. and
expressed in moles.l-1 ) and of calcium
hardness (in moles.l-1 ):
In this graph (see Figure 124), free CO2 and
pH are therefore represented by two sets of
parallel straight lines.
Free CO2 can be determined when the pH and
alkalinity of a water are known.
The graph contains two curves representing
physical dissolution of the CO2 and
neutralization by lime and limestone.
Figure 124 a shows an example of a water
in which the representative point M, defined
by its coordinates (M alk., pH), is located in
an aggressive zone. In order that it be brought
in line with the balance, three solutions are
possible:
- No. 1: escape of CO2 by aeration; the M alk.
and calcium remain unchanged; the saturation
pH thus corresponds to the pHs of the initial
water,
- No. 2: neutralization by a base (caustic soda
or lime); the M alk. rises and, if lime is used,
calcium rises in the same proportion,
- No. 3: neutralization by an alkaline
(Na 2 CO3 ) or alkaline-earth (CaCO3 )
carbonate; the M alk. and possibly (in the case
of CaCO3 ) the calcium increase approximately
twice as much as in the preceding case.
This demonstrates that on the one hand the
saturation pH is different in the three cases
studied, and that on the other hand the higher
the final M alk., the lower the saturation pH.
13. Neutralization - Remineralization
Chap. 3: Basic physical-chemical process in water treatment
13. Neutralization - Remineralization
Chap. 3: Basic physical-chemical process in water treatment
 13. Neutralization - Remineralization
In cases numbers two and three, the
difference between the final M alk. and the
initial M alk. makes it possible to determine
the amount of alkaline reagent to be used
after an evaluation of the shifting of the
equilibrium line which is tied to the
variation in the alkalinity/calcium ratio
during the neutralization process.
Although it introduces concepts of
calcium and total hardness, this method
does not take the total salinity or the
alkaline waters into account and only
covers waters with a low or moderate
mineral content.
13.1.2.3. Legrand and Poirier method
These authors considered the system of
coordinates. plotting Ca 2+ on the X-axis and
total CO2 on the Y-axis (see Figure 125).
They justified this choice with the
advantages it presented: the steps are
arithmetic (as a rule in millimoles.l-1 ),
which prevents the origins being shifted to
the infinite; the concentrations of all basic
elements show up immediately; the shifting
of the representative point of water occurs
almost always following the
 Chap. 3: Basic physical-chemical process in water treatment
lines or following the equilibrium curve.
Finally, the treatment process is shown on
this graph either by a displacement of the
representative point or by a change in the
equilibrium curve or by both at once.
Taking ,
the equation of the electric neutrality (1)
becomes: (H C03 -) = 2 [(Ca 2+) - ?] - 2 (C03 2-
) - (OH-) + (H+) and adding to each element
of the equation (H2 CO3 ) + (CO3 2-):
total CO2 =
2 [(Ca2+) - λ] + (H2CO3) - (CO32-) - (OH-) + (H+ )
In adopting the coordinates mentioned
above, a graph is obtained whose plane is
divided into areas limited by the main
particular cases (corresponding to the set of
curves pH = constant, which is a set of lines
coming together at point S of abscissa ~,):
Figure 125 illustrates these areas; practice
demonstrates that the near totality of natural
water (before or after treatment) is comprised
in area III, that
 13. Neutralization - Remineralization
is to say between the line of slope 4 (which
corresponds to pH = pK'i = about 6.4 at
20°C) and the line of slope 2 (which
corresponds to
The curve to which all the waters at
equilibrium relate for given values of
temperature and parameter λ, is the type
shown in Figure 126; this figure, among other
things, shows an example of figurative point
M of a given water, which is assumed to be
aggressive, with its position relative to the
equilibrium curve and data which may be
deduced as regards the characteristics of the
13.2.
ACHIEVING CARBONATE
BALANCE
First, it should be remembered that it is
sometimes possible to correct the pH value
by physical techniques involving gas and
liquid phase mass transfer.
Particularly the processes involving the
physical removal of carbon dioxide by
aeration are described in sub-chapter 14, and
so, only those cases which involve a chemical
reaction in water to be treated will be
considered here.
13.2.1. Addition of reagents
13.2.1.1. Neutralization through the
addition of alkaline or alkaline-earth
reagents
In the case of water intended for human
consumption, the reagents most commonly
used are caustic soda, lime or sodium
carbonate. The reactions of aggressive CO2
neutralization are therefore the following:
ater (particularly the proportion of aggressive
CO2 in the total free CO2 content).
The use of the graph makes it possible to
predict the development of the system in all
possible cases (with the amount of reagent
doses if necessary) with or without changes
in the equilibrium curve.
Apart from the Legrand and Poirier
method, there are hardly any other methods
that provide such thorough results. However,
this method involves long calculations.
Nonetheless, its use has been simplified and
expanded through the use of the micro data
processing.
2CO2 + Ca(OH)2 à Ca(HCO3 )2
CO2 + NaOH à NaHCO3
CO2 + Na 2 CO3 + H2 O à 2NaHCO3
These same products are used in the
treatment of industrial water, which also uses
other specific reagents:
- lithium hydroxide in the nuclear indus-
try,
- neutralizing amines (ammonia,
cyclohexylamine, ethanolamine, morpholine,
etc.) in boiler feedwater: during vapour
condensation they combine with the
dissolved carbonic acid to form an amine
bicarbonate; the coefficients of the division of
CO2 between vapour and water phases are
such that the applied dosages may be much
lower than the stoichiometric amounts
calculated based on the CO2 actually released
in the boiler; at low and medium pressures
the dosage is in the order of 1 g per g of
released CO2 ; at high pressure following
thermal deaeration, the dosages are about 1 g
per m3 of water,
 Chap. 3: Basic physical-chemical process in water treatment
- calcium carbonate in powder form for the
neutralization of industrial wastewaters.
With carbonic acid these reagents cause
the formation of bicarbonates. With strong
acids from some industrial effluents,
neutral salts are obtained.
Because of its low price, lime is the
reagent most frequently used. When lime is
used for the final adjustment of the pH
value in drinking water, it is useful to
employ a lime saturator to trap impurities
and to provide a limpid lime water,
whereas milk of lime always lends water a
turbidity whose intensity depends on the
degree of purity of the commercial product
and the required amount of lime.
All neutralization treatments must be
carefully monitored. It is often desirable to
slave the reagent dosage to the result ant
pH value in treated water. The efficiency of
the treatment also depends on how well the
neutralizing reagent is mixed with the
water to be treated: thus, it is important to
obtain an even mixture in reaction vessels
equipped with stirrers.
This type of neutralization in drinking
water treatment plants is carried out:
- either at the end of the treatment,
- or partly at the beginning. of the treatment
(adjustment of the flocculation pH value
for example) and continuing at the end of
the treatment line,
- or sometimes entirely at the plant inlet
(particularly in some cases of iron-
manganese removal).
13.2.1.2. Acidification
The main applications of this technique are
as follows: correction of scaleforming
water, "vaccination" of industrial systems,
treatment prior to desalination,
neutralization of alkaline effluents and pH
adjustment after softening by lime.
When CO2 is used, the plant comprises:
storage tanks or cylinders, a gas flowmeter
and a dissolving tower. In other cases
sulphuric acid and sometimes hydrochloric
acid are used and these are fed by metering
pumps.
13.2.1.3. Reciprocal neutralization
In some cases a chemical reagent may be
dispensed with, when using the interaction
of two or more waters with opposite
characteristics:
- aggressive waters and scale-forming
waters (however, additional reagent often
has to be added to achieve the exact
carbonate balance conditions),
- acidic and alkaline effluents (surface
treatment, for example).
In this category we can also include
those cases where acidic and alkaline
waters are passed alternately through
carboxyl resins.
13.2.2. Filtration on alkaline-earth
products
This type of treatment which uses
materials with a base of calcium carbonate
mixed, where appropriate, with magnesium
carbonate (dolomite) or magnesium oxide,
is most often applied to the neutralization
of aggressive carbon dioxide; the latter
forms bicarbonates during the filtration
process.
In the past it was common practice to
use marble as the filtering material.
However, because of its slow rate of
reaction other products known under the
commercial names of Neutralite, Neutralg,
 13. Neutralization - Remineralization

Magno, Akdolit, etc., are now preferred. (removal of iron and manganese from
The reaction kinetics of these agents give deep-lying water, clarification of surface
complete effectiveness with a relatively water, etc.).
small compact mass. However, with this procedure the
Some of the products available on the saturation pH cannot be exceeded to speed
market are calcined during their up the formation of the protective film
manufacture and therefore contain a high which may require the additional injection
proportion of alkaline-earth oxides and give of an alkaline reagent.
the treated water a high degree of alkalinity
when they are first put into service which 13.2.3. Consumption of reagents in the
gradually diminishes in the course of time. adjustment of carbonic acidity
Neutralite and Neutralg, with no free
bases, do not have these disadvantages and Consumption of Increase of
are indefinitely stable. They are available in Reagent pure product hardness
various grain sizes and are composed of per g of aggressive aggressive
C O 2,
calcium and magnesium carbonates. Their
CO2 in Fr. degrees
special structure insures a rapid and Lime 0.84 g Ca(OH)2 0.11
uniform solubility which is always (0.85-1 g of
proportional to the amount of C02 to be commer-
cial grade product)
neutralized.
Caustic 0.91 g NaOH 0
Filtration through alkaline-earth soda
materials is employed very often in deep- Sodium 2.4 g Na2 CO3 0
carbonate
lying water where no other treatment is
Marble 2.3 g CaCO3 0.23
required, while the addition of products in Magnesium 0.45 g MgO 0.11
slurry or solution form is generally oxide
incorporated in a complete treatment line Neurralite 2-2.2 g 0.23

13.3. quality of some waters used for

consumption (evaporator water).
REMINERALIZATION
This stage of treatment is generally
designed to take place at the end of the line
13.3.1. Purpose (fresh ground water or water having
undergone desalination treatment). It may
Remineralization results in an increase in als o be of use to enlist this treatment step at
the M alk. and/or the CaH. It is also the beginning of the line for fresh and
referred to as recarbonation. It is most often coloured surface water requiring a
used to promote the formation of a complete clarification treatment. This
protective film inside a pipeline. It may enables a better monitoring of the
also be used as an aid to help process water flocculation pH value and, if necessary, an
to meet the standards of quality or to improvement in the flocculation quality.
improve the organoleptic (and sanitary)
 Chap. 3: Basic physical-chemical process in water treatment
13.3.2. Process
To achieve the recommended and CaH
values, various techniques may be used
depending on the initial quality of the water,
the size of the plant and the treatment
materials that are locally available.
13.3.2.1. Carbon dioxide and lime
This is the technique most commonly used
when the quality of water requires that there
be a simultaneous increase of M alk. and
calcium in medium and largesize plants.
About 8.8 g Of CO2 + 5.6 g of CaO or 7.4 g
of Ca(OH)2 should be added per degree of M
alk. and per m3 of water.
The carbon dioxide is usually introduced
into the contact tower through porous
diffusers under a head of water several metres
high. In the case of water for industry, CO2
may be taken from engine exhaust or a flue
and, if necessary, scrubbed in a trickling
column. It is also possible to use submerged
burners to burn a liquid or gaseous
hydrocarbon in the liquid itself.
The quantities of fuel required to generate 1
kg of CO2 are: coke 350 g, fuel oil 450 g.
However, only commercial liquid CO2
ensures a higher-purity product (such as in the
case of drinking water).
The lime must be prepared in a saturator in
the form of lime water when a clear water is
being remineralized at the end of the
treatment line. Depending on the initial M alk.
of the water to be treated, it is sometimes
preferable to inject the lime following the
carbon dioxide to avoid removal of carbonates
from the water at the point of lime injection.
 13. Neutralization - Remineralization
13.3.2.2. CO2 and filtration through
neutralizing materials
In this case carbon dioxide consumption
is reduced (4.4 g.m-3 3 per degree of
remineralization) and the process runs more
smoothly. However, contrary to the CO2 and
lime processes, the saturation pH cannot be
exceeded, even when this is necessary.
13.3.2.3. Sodium bicarbonate and calcium
salt
HCO3 bicarbonate ions (as sodium
bicarbonate) and Ca 21 calcium ions
(generally as calcium chloride, though
sometimes as calcium sulphate) are
introduced into the water simultaneously.
To obtain an increase of 1 French degree
in 1 m3 of water, 16.8 g of sodium
bicarbonate must be used with either:
- 11.1 g of calcium chloride (as CaCl2 ),
- or 13.6 g of calcium sulphate (asCaSO4 ).
For this last process, unfired gypsum may be
placed in contact with the water in order to
prepare a saturated solution containing 2.3 g
of CaSO4 .2H2 O or 1.8 g of CaSO4 per litre.
Calcium chloride has the advantage of being
easier to use due to its solubility. However,
it introduces Cl- ions into the water which,
when added to a pre-existing concentration
that is already high, may reverse the effects
of the remineralization treatment by exerting
an influence on the corrosion processes.
Unless a high degree or
remineralizationization has been achieved,
this type of treatment usually must be
completed by an injection of an alkaline
reagent in order to reach the saturation pH.
These treat-
 Chap. 3: Basic physical-chemical process in water treatment

ments which require a small initial outlay
(preparation tanks and metering pumps)
lead, however, to high operating costs. These
techniques are usually used with small and
medium-size plants.
13.3.2.4. Miscellaneous
Depending on the quality of the water and
the availability of local materials, the
following techniques may sometimes be
employed:
- sodium bicarbonate + lime or sodium
carbonate
- sodium carbonate and carbon dioxide,
- sulphuric acid and calcium carbonate.