By: Teguh Indra Laksana

Buckman Treatment Guidelines – Boiler Water

The purpose of chemical treatment in boiler systems is three-fold:

Control corrosion in the feedwater system, the boiler itself and the condensate system
to protect the operational integrity of the equipment

Prevent the formation of deposits on boiler surfaces that would impede heat transfer

Insure that steam purity meets the criteria for its use

Impurities such as hardness, alkalinity, silica, oxygen, metal ions and organic material in
the boiler feed water will create the well known problems as boiler deposits, corrosion
and steam contamination. While it is the purpose of pretreatment equipment to remove
as many of these contaminants as possible, some may still enter the boiler system. A
properly designed treatment program will mitigate the impact of these impurities.

Treatment Program Parameters The parameters for proper boiler chemistry come
from a number of different sources. In the US, operating guidelines for boiler chemistry
come from the American Boiler Manufacturers Association (ABMA) and the American
Society of Mechanical Engineers (ASME). These guidelines are based on the type of
boiler (firetube versus watertube), operating pressure and whether there are restrictions
on steam purity due to superheaters or turbines. Since the guidelines from these two
organizations are similar, the ASME guidelines will be discussed.

Tables 1 and 2 are copies of the ASME charts for watertube boilers with steam purity
restriction and firetube boilers without restrictions. A number of comments are in order.

The values for various boiler operating parameters in these charts are driven
predominantly from the standpoint of steam purity. These include hardness, iron,
cooper, suspended solids, pH, organic mater, silica, alkalinity and conductivity.

In general, restrictions on both feedwater and boiler water become more stringent as
boiler operating pressure increases.

Oxygen limits are universally 7 ppb prior to the addition of chemical oxygen
scavenger and imply that a properly operating deaerator is present in the system.

These same guidelines apply regardless of the type of internal treatment chemistry
used to treat the boiler.

1
Table 1. ASME Consensus Guidelines for Water Tube Boilers

2
Table 2. ASME Consensus Guidelines for Firetube Boilers

3
Oxygen Scavengers

Oxygen scavengers are chemicals which are added to remove free oxygen from the water,
thus inhibiting corrosion by spontaneous reaction of metal surfaces with dissolved
oxygen. Some of these scavengers chemically react with oxygen directly to physically
remove it from the water. On the other hand, passivating chemistries act as corrosion
inhibitors through complex chemical interactions with system metallurgy.

Sulfite The most common chemical used to scavenge oxygen in low pressure boilers is
sodium sulfite. Sodium sulfite can be fed to a system in either a dry or liquid form; dry
sulfite products are typically in the form of sodium sulfite (Na2SO3) while liquid sulfite
products are solutions of either sodium bisulfite (NaHSO3) or sodium metabisulfite
(Na2S2O7). Regardless of their form, all of these materials react with oxygen as the
sulfite ion (SO3).

The basic reaction with oxygen is as follows:

2Na2SO3 + O2 2Na2SO4

The stoichiometry of the reaction is that it takes 7.9 ppm of Na2SO3 or 5 ppm of SO3 to
react with each ppm of oxygen (O2) that is present.

To make sure there is a sufficient amount of sulfite to drive the scavenging reaction to
completion, an excess of sulfite is kept in the system. This excess is maintained by
carrying a residual level of sulfite in the boiler water. The amount of excess is dictated
by the pressure of the boiler. Guidelines for sulfite residual are found in Table 3.

Table 3. Recommended Sulfite Residuals Based on Boiler Pressure

Boiler Pressure (psi) Sulfite Residual (ppm as SO32-)

150 30 – 60
300 30 – 40
600 20 – 30
900 10 – 15
>1200 Not Recommended

4
The application of sulfite as a boiler oxygen scavenger is limited by pressure due to its
thermal breakdown. The decomposition of sodium sulfite begins around 600 psi and will
impact steam purity at 900 psi. The breakdown products are volatile and acidic (H2S and
SO2) and results in highly corrosive steam and condensate if not neutralized:

Na2SO3 + H2O 2NaOH + SO2

4Na2SO3 + H2O 3Na2SO4 + 2NaOH + H2S

The reaction rate of sulfite with oxygen at room temperature can be increased with the
use of cobalt as a catalyst. At room temperature, catalyzed sulfite will remove all oxygen
in less than 30 seconds, while uncatalyzed oxygen only results in partial oxygen removal,
even after 30 minutes. The difference is reaction rates narrow as temperature is
increased, but even at feedwater conditions, catalyzed sulfite is preferred due to the short
reaction time available in real world systems. This is because the corrosion reaction at
the metal surface is faster than the reaction between sulfite and oxygen so it is imperative
than oxygen levels be driven to zero as quickly as possible. It is strongly recommended
that catalyzed sulfite be fed separate from all other treatment chemicals since the cobalt
will be precipitated at pH greater than 9.0 and can react with various other program
components.

As with all oxygen scavengers, the feed of sulfite should be continuous to the system.
The preferred injection point is the deaerator storage tank where a longer detention time
permits a better opportunity for complete oxygen removal. Liquid sulfite products are
acidic in nature and feed system components should be constructed of corrosion resistant
materials. Likewise, the use of an injection quill is critical to prevent low pH liquid
sulfite from contacting the metal surface of the system. Ideally, sulfite feed should be
fed through a “T” header to insure that good distribution of the oxygen scavenger in the
storage section.

Unlike many alternatives, sodium sulfite is suitable for use in plants that must meet FDA
guidelines for boiler water additives. While catalyzed sulfite is the preferred oxygen
scavenger for low pressure boiler systems due to its fast reaction time and low cost, there
are a number of limitations to its use. Sodium sulfite adds dissolved solids to the boiler
water and may contribute to higher blowdown rates and subsequent energy losses.
Because it adds solids to the water, sulfite may not be used in spray attemperation since it
would cause deposits on superheaters and turbines. For similar reasons, sulfite cannot be
used for boiler lay-up during storage if the boiler has non-drainable superheaters. Lastly,
sulfite is only an oxygen scavenger and shows no evidence of having metal passivating
properties.

5
Passivation Passivation is process by which the surface of a metal is converted into a
more stable, corrosion resistant layer as the result of chemical reactions between metal
ions and ionic or other chemical species in the aqueous medium. The passivation of steel
depends on the formation of a thin magnetite (Fe3O4) film, which is a magnetic and
electrically conductive black iron oxide. The passivation of copper and copper alloys in
absence of certain organic inhibitors depends on the formation of cupric oxide (CuO),
which is also a black material. Red cuprous oxide (Cu2O) is also protective but is not the
protective species formed in the absence of reducing agents.

Under boiler conditions, magnetite is naturally formed by the reaction of water with the
metal surface. Simply, the formation of magnetite occurs in two steps:

Fe + 2H2O Fe(OH)2 + H2

3Fe(OH)2 Fe3O4 + H2 + 2H2O

This is a simplification of the Schikorr reaction which describes the mechanism by which
magnetite is formed in pure water. The rate of magnetite formation is temperature
dependent and the reaction occurs spontaneously at temperatures above 360° F. The rate
of magnetite formation below this temperature is slowed due to the breakdown of the
intermediate hydroxide. This reaction can be promoted by certain oxygen scavengers
referred to as passivating agents. The exact mechanisms of how these materials foster the
formation of magnetite are not well known.

Since magnetite is the protective species of steel, the passivation of this material depends
on creating and maintaining an aqueous environment in which the magnetite is stable
with respect to reactions which would cause the protective barrier to dissolve or to be
converted into a more porous, and therefore, less protective form.

Hydrazine Because of the drawbacks associated with sulfite at higher pressures, a

number of alternatives are available for use. The most common of these is hydrazine.
Hydrazine (N2H4) can be used at all pressures and is suitable for use in water for steam
attemperation.

The reaction of hydrazine with water is shown in the following equation:

N2H4 + O2 N2 + 2H2O

It takes one ppm N2H4 (100%) to react with one ppm O2. This direct reaction with
oxygen is relatively slow below 300°F, but a number of catalysts can speed the reaction.
The presence of an iron or copper metal surface can enhance the reaction rate at lower
temperatures; additives such as hydroquinone can also have a catalytic effect. In boiler
systems, the interaction between hydrazine and the metal surface enhances metal
passivation,

6
Hydrazine has a number of downsides to its use. Hydrazine has significant toxic
properties and is classified as a suspected carcinogen. As a result, most industrial
locations have banned the use of hydrazine. It can be found in high pressure utility
operations where closed transfer and dosing systems are employed and employee health
is monitored.

Besides the negative health aspects, one of the decomposition products of hydrazine is
ammonia (NH3). This breakdown becomes significant at temperatures above 200° C.

3 N2H4 4NH3 + N2

In the presence of oxygen, ammonia levels of 0.2 ppm will attack copper metallurgy in
the boiler system.

Organic Scavengers Due to some of these undesirable characteristics, a number of

hydrazine alternatives have been developed.

Diethylhydroxylamine (DEHA) has a number of distinct advantages for use in industrial

systems. The basic reaction with oxygen can be described by the following equation:

4(CH3CH2)2NOH + 9O2 8CH3COOH + 2N2 + 6H2O

This reaction indicates that DEHA stoichiometry with oxygen is 1.24 ppm per ppm O2 if
the molecule was oxidized completely to acetic acid. However, the actual oxidative
pathway is much more complex and never goes to completion as indicated above when a
residual is maintained in the water.

When DEHA is added to water in the presence of oxygen, a series of reactions take place.
The first step in the DEHA reaction with oxygen is the formation of an intermediate
nitrone:

2(C2H5)2NOH + O2 2CH3CH=N(O)C2H5 + 2H2O

(DEHA) (Nitrone)

The nitrone is very unstable and quickly reacts with water to form ethylhydroxylamine
and acetaldehyde:

CH3CH=N(O)C2H5 + 2H2O 2C2H5N(OH)H + 2CH3CHO

(Nitrone) (Ethylhydroxylamine) (Acetaldehyde)

The resulting ethylhydroxylamine is also a good reducing agent and scavenges additional
oxygen as follows:

2C2H5N(OH)H + O2 2CH3CH=NOH + 2H2O

(Ethylhydroxylamine) (Acetaloxime)

7
The acetaloxime formed is a weak reducing agent and will not scavenge oxygen directly.
Instead it reacts with water to form acetaldehyde and hydroxylamine:

2CH3CH=NOH + 2H2O 2CH3CHO + 2H2NOH

(Acetaloxime) (Acetaldehyde) (Hydroxylamine)

The hydroxylamine formed in this reaction will then react with more oxygen:

2NH2OH + ½O2 N2 + 3H2O

(Hydroxylamine)

The acetaldehyde can also react with oxygen to form acetic acid:

4CH3CHO + 2O2 4CH3COOH

(Acetaldehyde) (Acetic Acid)

This last reaction is extremely limited is any other molecules in the preceding reactions
are present. Taking the overall reactions of DEHA into account, the stoichiometry with
respect to oxygen scavenging is 3 ppm DEHA per ppm O2.

DEHA is also subject to thermal decomposition. At temperatures in excess of 288°C,

DEHA will breakdown into smaller amines and some ammonia, but to a considerably
lesser extent than hydrazine.

From an oxygen scavenging perspective, sodium sulfite is a much faster oxygen

scavenger than any of the organic chemistries. However, DEHA catalyzed with
hydroquinone is a extremely effective alternative compared to hydrazine. Figure 1.
shows a comparison of DEHA to sulfite and hydrazine under feedwater conditions.

100
)
% Oxygen Removal

0 °C

A
80 DEH
(9
te

A
H
lfi

DE
Su

60 °C)
(90
d
um

ze

i n e
ly

raz
di

ta

Hyd
So

40
Ca

(25°C)
Hydrazine
20

0
0 2 4 6 8 10

Time (minutes)

Figure 1. Comparison of O2 Scavenging Rates

8
In addition to its ability to scavenge oxygen, DEHA is a strong reducing agent that
promotes passivation of metal surfaces through the formation of magnetite. This
characteristic has been demonstrated in the laboratory in electrochemical polarization
studies as well as in real world applications. A well passivated metal surface has a much
lower overall corrosion rate and will result in reduced levels of metal oxide corrosion
products being liberated into the water.

In addition to O2 scavenging and metal passivating capabilities, another critical

characteristic of DEHA is its volatility. When fed to boiler feedwater, DEHA will
volatilize with the steam. Not only will this chemistry passivate the boiler feedwater
system, it will also be distributed throughout the condensate system (vapor-liquid
distribution ratio of 1.26) to protect it as well against corrosion.

While DEHA is an amine, it has very low neutralizing capacity compared to standard
amines used for condensate treatment. However, it has been observed in practice that
DEHA can have a beneficial effect on condensate pH. In some cases, it may be possible
to reduce the overall amount of amine being fed while maintaining pH and system
protection as reflect in measured levels of dissolved and suspended iron in the return
condensate.

Being organic in nature, DEHA does not contribute to solids in the water and thus can be
used in spray attemperation applications. DEHA has been successfully used in boilers
operating at pressures greater than 2000 psi. However, DEHA is not acceptable for use
in plants subject to restriction under 21 CFR § 173.310.

Carbohydrazide (CHZ) is a hydrazine substitute that acts like hydrazine under system
conditions but has reduced hazards associated with its use.

When added to water at 150° C or greater, carbohydrazide will begin to decompose

according the following reaction:

(N2H3)2CO + H2O N2H4 + CO2

The hydrazine formed is then available to react with the oxygen present. On a theoretical
basis, it takes 1.5 ppm of carbohydrazide to react with 1 ppm O2. It is of interest to note
that an additional 0.7 ppm of CO2 is liberated, which needs to be accounted for when
calculating neutralizing amine requirements.

At temperatures below that needed for hydrolysis to form hydrazine, it is claimed that
carbohydrazide reacts directly with oxygen.

The reaction of carbohydrazide with oxygen is catalyzed by traces of transition metal

salts or hydroquinone which are also known to catalyze the corresponding reaction of
hydrazine. Its pH dependence is similar to that of hydrazine.

9
At normal industrial boiler pressures, carbohydrazide is not volatile and will remain in
the boiler. However, it does not add solids to the water and thus is suitable for use in
steam attemperation. It is not FDA approved.

Ascorbic Acid and Erythorbic Acid Ascorbic acid (vitamin C) and erythorbic acid (its D
isomer) are organic acids that act as oxygen scavengers. Their primary advantage is their
GRAS (Generally Recognized as Safe) which permits their use in applications where
boiler water may come in contact with food.

It requires 11 ppm of either ascorbic or erythorbic acid to react with 1 ppm O2. The
reaction rate of these materials is pH sensitive and fastest when the pH is above 9.5. As
acids, these materials have a low pH and must be buffered with amine or ammonia to
prevent pH depression of the system.

At temperature of 500°F, either acid will thermally decompose to carbon dioxide and
water. For this reason, the use of these materials is acceptable for systems with steam
attemperation. However, they are not volatile and thus remain in the boiler and afford no
downstream protection. In high pressure applications, cases of severe pH depression
have been reported when overfed. They are not recommended for boiler storage
applications.

Methyl Ethyl Ketoxime (MEKO) is another organic chemistry that has been used for
oxygen scavenging. In many respects, it is similar in properties to DEHA in that it
promotes passivation and is volatile. It is of interest to note that one of the intermediate
reactions with DEHA is the formation of an oxime which forms hydroxylamine. Its
oxygen removal performance is faster than DEHA but is not as good a passivator. It
forms only volatile reaction products and thus the potential for organic acid formation is
eliminated.

The basic reaction of MEKO with oxygen is described by the following equation:

2(CH3) (CH3CH2)C=NOH + O2 2(CH3CH2)C=O + N2O + H2O

It requires about 5.4 ppm MEKO to scavenge 1 ppm O2. MEKO has vapor-liquid
distribution ratio of 9.8 and does not contribute solids to the boiler water.

Above 300°C, MEKO decomposes to methyl ethyl ketone (MEK), nitrous oxide,
nitrogen, ammonia and traces of carbon dioxide.

Internal Treatment

The primary purpose of internal treatment is the control of deposition on heat transfer
surfaces and maintenance of conditions to prevent corrosion of the boiler. Much of the
initial technology for boiler water treatment was developed for the treatment of steam
locomotives. Since modern pretreatment methods such as ion exchange were not yet

10
available, these programs involved softening the water using additives such as soda ash
and sodium aluminate.

Deposit control programs basically fall into two broad categories of approaches. The first
group is precipitation type programs which include the carbonate cycle and phosphate
residual programs. The intent of these programs is to form a sludge that was easily
conditioned and removed by boiler blowdown. The other approach to deposit control is
the solubilization type program. These programs are designed to complex hardness
before it gets to the boiler and keep it soluble until removed by blowdown. Chelant-
based and all organic programs are the two predominant types of solubilization
chemistries.

Carbonate Cycle Carbonate precipitation programs have been used for years to treat
low pressure boilers with feedwater hardness in excess of 50 ppm. In boilers with no
pretreatment equipment, the predominant scale forming material is calcium sulfate which
forms a hard, insulating, and difficult to remove deposit. To prevent the formation of
sulfate salts, sodium carbonate would be added to form calcium carbonate since it has a
lower solubility than its sulfate counterpart. An excess of carbonate is carried in the
boiler water to drive the preferred reaction to completion. The breakdown of carbonate to
form OH alkalinity would then react with magnesium to form magnesium hydroxide.

Before the advent of polymers, it was found that the inclusion of certain types of organics
would help condition the sludge and reduce the amount that would deposit in the boiler.
Materials such as tannins and lignins were used for that purpose. The use of polymers
greatly improves the cleanliness of carbonate cycle treated boilers.

There are a number of operating problems encountered in carbonate cycle programs. In

very hard waters, the shear volume of sludge produced results in poor results. In very
low pressure boilers, supplemental caustic may be required since carbonate may not
breakdown sufficiently to provide enough hydrate needed to react with all the magnesium
present and lead to the formation of calcium or magnesium silicate deposits. If
deaeration is poor or non-existent, the amount of sulfite required to scavenge oxygen may
lead to too high levels of dissolved sulfate which may still cause calcium sulfate to form.
Sulfate level in the boiler must be limited to 500 ppm. This type program is limited to
boilers operating below 150 psig. At pressures higher than these, too much of the sodium
carbonate fed will breakdown to hydroxide, leaving insufficient carbonate to react with
the calcium present.

The prevalence of softeners on most low pressure systems have reduced the use of
traditional carbonate cycle programs where supplemental sodium carbonate is added.
Under these conditions, the natural alkalinity of the make-up water supplies enough
bicarbonate and carbonate in relation to the hardness in the softened water to prevent
calcium sulfate formation. When feedwater hardness is properly controlled, the
application of polymer-based sludge conditioners can result in excellent boiler cleanliness.

11
Phosphate Residual The addition of phosphate to boiler water prevents the formation
of calcium salts of sulfate, silicate and carbonate since calcium phosphate is even less
soluble. In the presence of sufficient hydroxide alkalinity, the actual phosphate
precipitate formed is hydroxyapatite, which is a less sticky and more readily conditioned
than tri-calcium phosphate. The presence of OH is also critical to prevent the formation
of either magnesium phosphate or silicate which are more difficult to condition. While
Mg(OH)2 is the preferred precipitate, serpentine may be formed when magnesium and
silica levels in boiler feedwater are high.

For phosphate residual programs, the desired reactions with hardness contaminants are as
follows:

10Ca2+ + 6PO43- + 2OH- 3Ca3(PO4)2 . Ca(OH)2

Mg2+ + 2OH- Mg(OH)2

3Mg2+ + 2SiO23- + 2OH- + H2O 2MgSiO3 . Mg(OH)2 . H2O

Several forms of phosphate can be used to precipitate calcium. Either orthophosphate in

the form of a sodium salt or various polyphosphate may be used are the phosphate donor.
Polyphosphate is a polymer of two or more orthophosphate groups. The type of
phosphate used is dictated by its addition point to the system as well as the alkalinity of
the feedwater. The formation of calcium phosphate can only occur when the phosphate is
present in the orthophosphate form. If the phosphate is fed to the steam drum,
orthophosphate is the preferred form since it will be readily available to react with
hardness present. However, if applied to the feedwater line, a polyphosphate is preferred
to prevent reaction with hardness before it enters the boiler. When the polyphosphate hits
the boiler water, the combination of heat and high pH causes rapid breakdown into the
orthophosphate form. Hydroxide alkalinity is consumed when polyphosphate hydrolyses
to the orthophosphate.

A surplus of phosphate should be maintained in the boiler water to act as a reserve

against sudden increases in feedwater hardness. When controlling the amount of
phosphate in the boiler, it is important that phosphate tests be conducted on filtered
samples to prevent interference from precipitated hardness. Table 4 lists some guidelines
for the amount of residual phosphate that should be maintained in the boiler water.
Phosphate residual control ranges can be reduced from these numbers if the feedwater
quality and consistency permit. Phosphate levels of greater than 60 ppm should be
avoided since the potential of adherent magnesium phosphate is greatly increased. The
suggested levels of OH alkalinity needed to drive the desired reactions are also dependent
on boiler pressure and are listed below as well.

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 Table 4. Phosphate and Hydroxide Residuals for Boilers with Soft Water Makeup

Drum Pressure Phosphate OH Alkalinity

(psig) (ppm as PO4) (ppm as CaCO3)
0 – 300 30 – 60 200 – 300
300 – 600 20 – 40 150 – 200
600 – 900 15 – 20 120 – 150
900 -1200 10 – 15 100 – 120

Polymer Dispserants In a phosphate treatment program where hardness is being

precipitated, suspended solids (or sludge) will be forming constantly. In addition,
corrosion by-products consisting of particulate metal oxides are returned to the boiler via
condensate adding to suspended solids. These insoluble materials can affect both boiler
cleanliness and steam purity. Depending upon their composition, suspended solids
exhibit varying tendencies to deposit on boiler heat transfer surfaces.

The addition of organic polymers to condition the hardness and iron precipitants is vitally
important in preventing the formation of heat insulating deposits. Natural organics such
as tannins and lignins have given way to synthetic polymers with improved performance.
Materials such as polyacrylic acid and acrylate-acyrlamide copolymers prevent
deposition via two different mechanisms. First, they act by charge reinforcement to add
more negative surface charge to increase the repulsion forces that minimize particle size.
Second, they act as threshold inhibitors via crystal modification to distort the morphology
of the precipitants and reduce their tendency to stick to boiler surfaces.

Typical level of active polymer required to condition sludge is between 10 and 20 ppm,
dependent on the amount of solids present and the type of polymer used. Insufficient
levels of polymer may lead to the formation of deposits despite good blowdown practice.
Dispersants should normally be fed to the boiler feedwater as far ahead of the boiler as
possible to maintain the maximum cleanliness of the pre-boiler (feedwater system). The
preferred feed points are to the deaerator storage compartment or to the boiler feedwater
line as far ahead of the boiler drum as possible. Direct feed to the boiler drum is
generally not recommended.

The use of phosphate residual programs is generally limited to feedwater hardness of 10

ppm due to the volume of solids that are formed. Regardless of the type of internal
treatment program used, the better the feedwater quality entering the boiler, the better the
resulting boiler cleanliness.

Chelant Programs While precipitation programs purposely form insoluble compounds

from feedwater impurities, chelation keeps these same ions in solution by forming a
stable, complex ion. As a result, these cations are unavailable to react with the

13
appropriate anion to produce scale. For this reason, chelation is referred to as
solubilization chemistry.

Ethylenediamine tetra acetic acid (EDTA) is the most commonly used chelating agent.
The structure of EDTA is shown in Figure 2. It reacts stoichiometrically with calcium
and other cations to form soluble complexes that effectively prevent calcium carbonate
and sulfate, magnesium hydroxide and silicate, and soluble iron and copper from
precipitating in the boiler. It does so by blocking the reactive sites of the metal ion,
preventing them from entering into normal precipitation reactions.

O O
=

=
HO – C – CH2 CH2 – C – OH
N – CH2CH2 – N
HO – C – CH2 CH2 – C – OH

=
=

O O

Figure 2. Diagram of EDTA molecule

It takes about 3.8 ppm of tetrasodium EDTA (Na4EDTA) to react with 1 ppm of calcium
hardness.

EDTA is susceptible to thermal breakdown, beginning around 300 psi with significant
decomposition at 600 psi. However, complexes formed below these pressures are stable
at pressures at high as 1200 psi. Therefore, testing of free (unreacted) EDTA in the boiler
water is problematic above 600 psi and thus chelant should be fed based on feedwater
demand to the feedwater.

EDTA must be fed with a quill to keep the concentrated feed stream away from the walls
of the feedwater line due to the corrosivity of EDTA toward iron. It should be fed after
the boiler feedwater pump, since copper alloys such as bronze commonly used for pump
impeller construction can readily be attacked. It is imperative that feedwater oxygen be
zero with residual oxygen scavenger present at the point of injection since chelant will
greatly enhance the rate of feedwater oxygen corrosion. Care must be taken when feeding
chelant in systems with economizers, since they can be especially susceptible to oxygen
attack. EDTA should never be fed directly to the boiler as high localized concentrations
could result in corrosion damage.

When running a free residual program at lower pressures, normal residuals are kept in the
3 – 6 ppm range with other control parameters consistent with boiler pressure limits.
Under no circumstances should free EDTA residual ever exceed 20 ppm due to corrosion
concerns.

The low level of residual does not provide the same level of reserve that a phosphate
residual program does to handle feedwater upsets. When feedwater quality is well

14
controlled, chelant based programs can result in boilers of exceptional cleanliness. It is
common for chelant programs to be run on a sub-stoichiometric basis, i.e. enough EDTA
is fed to complex 80 – 90% of the hardness present, with the balance being treated with
threshold inhibitors and dispersants. This approach can reduce the potential for chelant
based corrosion.

All Organic Programs This type of approach uses a combination of solubilization for
hardness and dispersion for iron and other particulate material. Solubilization is
accomplished by polymers with carboxylate functionality that complexes the hardness
much like a chelant. Dispersion of iron and other particulates involves adsorption of the
polymer on their surface which increases surface charge repulsion and minimizing
agglomeration. These are the same types of polymers that are used as dispersants in
phosphate residual programs. A blend of different polymers is typically employed to
provide the proper balance between solubilization and dispersion effects. Unlike
chelants, the polymers are not aggressive towards iron and thus corrosion potential is
virtually zero even under overfeed conditions.

In addition to polymers, these treatments often incorporate a phosphonate such as HEDP

(hydroxyethylidene diphosphate) in their formulation. The phosphonate will function to
complex hardness and soluble iron by sequestration. When present in excess, it will also
act as a crystal modifier to provide added protection against temporary system upsets.
HEDP will also act as a buffer against the potential for calcium acrylate deposits when
severe upsets or under-dosing occurs.

The feedrate of all-organic programs should be based on the highest expected level of
feedwater impurities. Program feed rates are proportional to the level of impurities
present. As a general target, between 10 and 20 ppm of active polymer should be present
in the boiler, but this can change based on feedwater quality and boiler cycles of
concentration. Cycles normally should be limited to 50 cycles in industrial boilers, since
higher cycles reduce blowdown and increase holding time and the potential for thermal
degradation of program components. Other control parameters should be appropriate for
the boiler operating pressure. These programs are generally limited to 600 psig with soft
water make-up. While the polymers in the program are stable at higher pressures, the
HEDP will breakdown into phosphate and its functional effectiveness will be lost.

15
Interpretation of Deposits Collecting deposits for analysis during boiler inspections can
provide insight to the deficiencies of a boiler treatment program, but it is difficult to
correctly interpret their root cause from just the deposit analysis report. Constituents found
in a deposit analysis may be expected in one situation, but not under different operating
conditions. For example, a deposit containing a high percentage of phosphate might be
expected when using a phosphate residual program, but not if the boiler was being treated
with an all-polymer approach.

There are many factors to consider when interpreting any deposit analysis, such as:

Where was the deposit found?

How much deposit was present?
Based on prior inspections, is the level of deposition increasing or decreasing?
Was the deposit localized to a particular area or was it present in all boiler sections?
In a multi-boiler system, what is the condition of the other boilers?
How is the control of feedwater quality?
Is the condensate subject to contamination?
Is treatment program control adequate?
How and where is the treatment program fed?
Are there deposits on the fireside surfaces?

16
To assist in interpreting the why certain constituents of a deposit may be present, Tables 5
through 7 list the common reasons for phosphate, chelant and all organic programs.

Table 5. Deposit Interpretation for Phosphate Programs

Expected Conditions Generally Resulting in Abnormal
Composition Normal Amount
Percentage

Loss on ignition Usually 8-12%, except Low % indicates underfeed of organic; high % may
higher in very pure indicate organic overfeed or extraneous organic
feedwaters contamination.
Silica Low (usually <10%) High SiO2; low hydroxide alkalinity; intermittent steam
blanketing.

Alumina Low (usually <10%) Possible steam blanketing caused by soluble aluminum in
feedwater.

Iron oxide Low (usually <5%, High feedwater iron; corrosion in condensate, preboiler
(Fe2O3 or Fe3O4) except in high-purity system or boiler.
waters)

Basic calcium High (variable) % expected to be high; if volume of deposit abnormal may
phosphate indicate poor sludge conditioning, increased feedwater
hardness, or insufficient blowdown.

Magnesium Low (usually <5%, Too high phosphate residual; hydroxide alkalinity too low;
phosphate except in some high- silica too low; poor mechanical distribution of chemicals
pressure boilers) and/or feedwater in boiler.

Calcium carbonate Low (usually <5%) No phosphate residual.

Calcium silicate Trace or none No phosphate residual; low hydroxide alkalinity.

Magnesium silicate Moderate (low to high) % expected to be moderate; if volume of deposit high may
indicate poor sludge conditioning and/or too high
feedwater hardness.

Magnesium Moderate (low to high) Same as for magnesium silicate.

hydroxide

Sodium salts Low (usually <1%) Evaporation to dryness.

Calcium sulfate None No phosphate residual.

Calcium hydroxide None Calcium soap; calcium oxalate from sugar contamination;
overheating of calcium carbonate scale; free lime from
poor lime softener operation.

Copper Low (except may be high High feedwater copper; corrosion in condensate or
with high purity preboiler system.
feedwater)

17
 Table 6. Deposit Interpretation for Chelant Programs

Expected Composition Conditions Generally Resulting in

Normal Amount
Abnormal Percentage

Loss on ignition Varies due to water of hydration High % may indicate oil or other organic
associated with iron deposits contamination in feedwater.
Silica Low (<10%) High % may indicate improper OH control,
steam blanketing, improper demineralizer
operation or improper blowdown.
Iron oxide (Fe2O3 or High (> 50%) The deposit should be mainly iron but the
Fe3O4) amount should be small. Large amount of
deposit indicates high feedwater iron levels
due to corrosion in the condensate system
or preboiler system. May also be due to
internal corrosion.
Calcium phosphate None Old scale or phosphate contamination of
the feedwater.
Magnesium phosphate None Same as for calcium phosphate.
Calcium carbonate None Insufficient dosage due to increased
feedwater total acid hardness.
Calcium silicate None Low OH alkalinity with high boiler silica
and underfeed of chemical. Extremely high
heat transfer rates.
Magnesium silicate Low (<5%) High feedwater silica and magnesium
levels combined with chemical underfeed
and low OH alkalinity.
Sodium salts None Evaporation to dryness.
Calcium sulfate None Gross underfeed of chemical.
Copper Low High feedwater copper indicates corrosion
in condensate or preboiler system.

18
 Table 7. Deposit Interpretation for All-Organic Programs

Conditions Generally Resulting

Expected Composition Normal Amount in Abnormal Percentage

Loss on ignition Varies due to water of hydration High % may indicate oil or other organic
associated with iron deposits contamination in feedwater. If calcium
oxide is present, calcium acrylate may be
present due to gross underfeed of product.
Also, may indicate that a dirty boiler was
started on program causing acrylate to react
with existing mineral scale.
Silica Low (< 10%) High % may indicate improper OH control,
steam blanketing, improper demineralizer
operation, or chemical underfeed.
Iron oxide (Fe2O3 or High (> 50%) The deposit should be mainly iron, but the
Fe3O4) volume of iron should be small. A large
volume of iron indicates corrosion products
from the condensate, preboiler system, or
the boiler internals, coupled with an
underfeed of product and/or an insufficient
blowdown rate.
Calcium phosphate None Old scale or underfeed of product.
Feedwater contamination with phosphate.
Magnesium phosphate None Same as for calcium phosphate.
Calcium carbonate None Same as for calcium phosphate.
Calcium silicate None Same as for calcium phosphate.
Magnesium silicate None Old deposits, underfeed of product, low
alkalinity levels, or high feedwater silica.
Calcium oxide None If loss on ignition is high, gross underfeed
of product causing calcium acrylate
formation.
Sodium salts None Evaporation to dryness.
Calcium sulfate None Low OH- alkalinity and product underfeed.
Copper None low Copper or yellow metal corrosion in the
condensate or preboiler system.

19
Corrosion Control In High Pressure Boilers As boiler pressure and heat transfer
rates increase, corrosion of boiler tubes due to caustic becomes a problem. Even with
very low levels of free OH alkalinity in the boiler water, caustic can increase many orders
of magnitude at the tube surface due to the presence of departure from nucleate boiling or
underdeposit concentration mechanisms. While normal levels of boiler water hydrate
alkalinity are harmless to boiler steel, localized concentrations of several thousand ppm
or more are very aggressive to tube metallurgy. At such points, the protective magnetite
film is dissolved and corrosion of the tube metallurgy will occur, eventually leading to
failure. Low alkalinity boiler water treatment programs, such as coordinated phosphate
– pH or All Volatile Treatment (AVT) approach, are required to limit or eliminate the
presence of free hydrate alkalinity in the bulk boiler water.

Coordinated Phosphate-pH The objective of phosphate-pH control is to control the

amount of free hydroxide in the boiler water that could concentrate at the tube metal
surface. It is based on the fact that the addition of sodium phosphate to pure water creates
a pH buffering system. When disodium phosphate (DSP) is added to water, it will
consume any free caustic present during its conversion to trisodium phosphate (TSP):

Na2HPO4 + NaOH Na3PO4 + H2O

While this reaction describes the basic concept of phosphate-pH control, the underlying
chemistry is a bit more complex. Many phosphates can be used in various combinations
to achieve the concept described. The sodium orthophosphates (mono-, di- and tri-) are
all derived from the reaction of phosphoric acid with caustic. The addition of any one of
these orthophosphates to water produces a hydrolysis reaction that yields a phosphate ion
species, hydrogen or sodium ions, or hydroxide ions. The following set of reactions
illustrated this and shows the differences in buffering and pH effect:

Phosphoric acid: H3PO4 + H2O HPO4-2 + 2H+ + H2O

Monosodium Phosphate: NaH2PO4 + H2O HPO4-2 + H+ + Na+ + H2O

Disodium Phosphate: Na2PO4 + H2O HPO4-2 + 2Na+ + H2O

Trisodium Phosphate: Na3PO4 + H2O HPO4-2 + 3Na+ + OH-

Sodium Hydroxide: NaOH + H2O OH- + Na+ + H2O

As Figure 3 shows, the addition of a sodium phosphate at boiler water pH below the point
at which hydroxide is present will result in the dibasic anion (HPO4-2) being formed.

20
 Figure 3. Distribution of phosphate ionic species based on pH

At a pH between 9 and 10, tribasic phosphate hydrolyzes completely, with one mole of
trisodium phosphate increasing boiler water pH equivalent to the addition of one mole of
sodium hydroxide. Dibasic phosphate neither hydrolyzes nor dissociates appreciably in
this pH range; therefore, additions of disodium phosphate have little effects in pH.
Monobasic phosphate dissociates to the dibasic form; thus, a one mole addition of
monosodium phosphate is capable of neutralizing one mole of sodium hydroxide or one
mole of trisodium phosphate. Thus, the resultant boiler water pH from the addition of the
various orthophosphates is comprised of sodium and phosphate in various molar ratios. It
is common practice to describe a particular phosphate, or a mixture of phosphates,
according to the sodium-to-phosphate mole ratio (Na:PO4).

Table 8. Na:PO4 Ratios of Sodium Phosphates

Sodium to Phosphate
Type of Phosphate
Molar Ratio
Na3PO4 (TSP) 3:1
Na2HPO4 (DSP) 2:1
Na2H2PO4 (MSP) 1:1

At a 3:1 mole ratio or greater, the equivalent of trisodium phosphate plus caustic exists in
boiler water. Between a Na:PO4 between 2:1 and 3:1, a mixture of disodium and
trisodium phosphate is present. Thus, the captive alkalinity zone where free caustic is
absent is below a 3:1 Na:PO4 ratio.

Control Range The traditional control chart for coordinated phosphate is shown in
Figure 4. The operational zone with respect to phosphate and pH is typically dictated by
boiler pressure. The control vectors provide direction in correcting a transient boiler
water pH. By locating the current PO4/pH coordinates, a directional vector can be
obtained that will suggest the action required to bring the boiler back into range.

21
 10.8

10.6
Free t io
10.4 Caustic Ra
la r
Region Mo
/P O 4
10.2 :1 Na O 4 < 900 psi
3.0 a/P
ry :1 N
nda 2.8
u
10.0 m Bo
xi mu
Ma 900 – 1500
9.8
psi “Captive”
pH @ 25°C

/ PO
4
Na Alkalinity
9.6 2 .7:1
Region
tio
1500 – 2000 Ra
9.4 lar
Mo
psi /PO 4
9.2 / PO
4 Na
Na .2:1 NaOH
.6:1 y2
2 dar TSP
2000 – 2500 o un
9.0 ol B
psi ntr
Co
8.8 Blowdown DSP
> 2600 psi
8.6

Vector Control
8.4
Diagram MSP

8.2
1 2 3 4 5 6 7 8 10 15 20 30 40 50 60

Orthophosphate, ppm as PO4

Figure 4. Coordinated PO4 pH control curve

All Volatile Treatment (AVT) AVT is a means for achieving sufficiently high pH for
the protection of boiler steel without the introduction of any dissolved solids. These
programs utilize all volatile chemistries such as hydrazine for oxygen scavenging and
morpholine or ammonia for cycle pH control. The treatment concept may be employed
in boilers operating above 1800 psig and is the only program that can be used in utility
once-through boilers. In drum-type boiler cycles, AVT may be used for simplicity where
phosphate hideout has caused control problems on coordinated phosphate-pH programs,
or where ultra-pure steam is required.

A disadvantage of all-volatile treatment for drum-type boilers is that the boiler water is
unbuffered and thus subject to extensive and rapid pH excursions in the event of
feedwater contamination. With volatile treatment, the feedwater must be of the highest
purity and completely free of hardness or other dissolved solid constituents. Since no
phosphate or alkalinity is present to react with hardness, any contamination has major
reliability ramifications. A mixed bed polisher for make-up water and condensate
polishing system, either for continuous polishing or for start-up and emergency polishing,
is essential to proper operation.

22
Condensate Treatment

There are two basic approaches to controlling condensate corrosion. The first involves
the use of external means such as ion exchange or membrane separation and deaeration to
reduce the amount of alkalinity and dissolved gases in the boiler feedwater. The most
important method for controlling potential carbon dioxide content in the condensate
system involves alkalinity reduction in the feedwater. As discussed previously, the
majority of carbonic acid generated in the condensate results from the thermal breakdown
of bicarbonate and carbonate alkalinity. Control of dissolved oxygen in the feedwater is
normally achieved through a properly functioning deaerating heater together with
residual oxygen scavenger for the remaining oxygen that remains.

The second approach, which is necessary in all systems, involves the application of
chemicals to the steam leaving the boiler to counteract the corrosive effects of CO2,
ammonia, and oxygen. The treatment approaches incorporate the use of neutralizing
amines, passivating agents and organic filming inhibitors.

Neutralizing Amines Neutralizing amines are nitrogen containing compounds which

are added to steam systems to first neutralize carbonic acid that is formed and then raise
condensate pH. These amines offer no protection against oxygen attack. Neutralizing
amine programs are most effective when the pH of the condensate is controlled in the
range of 8.5 – 9.0. This range will maximize corrosion protection since CO2 does not
exist above pH 8.3 and overall corrosion rates of mild steel is reduced. Maximum
protection of copper alloys is also maintained in this range.

Neutralizing amines are added in direct proportion to the amount of carbon dioxide in the
steam. Therefore, in high alkalinity feedwater systems where CO2 generation is
appreciable, excessive amounts of neutralizing amines may be required to neutralize the
carbonic acid that is produced.

Neutralizing amines react with carbonic acid to form amine bicarbonates and amine
carbonates according the generalized equations below:

RNH3+ + HCO3- RNH3HCO3

2RNH3+ + CO32- (RNH3)2CO3

The capacity of a given neutralizing amine to react with CO2 is dictated by the equivalent
weight of the amine. The equivalent weight is calculated by dividing the molecular
weight by the number of amine functional groups in the molecule. The neutralizing
capacity of commonly used amines is listed in Table 9.

23
 Table 9. CO2 Neutralizing Capacity of Common Amines

Equivalent
Amine ppm CO2/ppm Amine ppm Amine/ppm CO2
Weight
DEAE 117 0.376 2.66
Cyclohexylamine 99 0.444 2.25
MOPA 87 0.494 2.02
Morpholine 87 0.506 1.98
Ammonia 17 2.60 0.38

Once all the carbonic acid present has been neutralized (pH = 8.3), additional amine will
raise the pH of the condensate. The ability of an amine to raise pH is given by its basicity.
The basicity is calculated using the following equation:

RNH2 + H2O RNH3+ + OH-

[RNH3+] [OH-]
Kb =
[RNH2]

How larger the Kb value, the stronger a base the amine is and the greater its impact on pH.
The basicity constants for common amines are shown in Table 10.

Table 10. Basicity Constants for Common Amines

Amine Basicity Constant

DEAE 5.2 x 10-5
Cyclohexylamine 4.4 x 10-4
MOPA 1.0 x 10-4
Morpholine 2.4 x 10-6
Ammonia 1.8 x 10-5

24
Volatility is another important attribute to neutralizing amines. Every gas in a condensate
system has a specific volatility or vapor to liquid distribution ratio (V/L). For a particular
substance, its distribution ratio is defined by:

[Concentration in the vapor phase]

[Concentration in the liquid phase]

The concept of distribution ratio is depicted in Figure 5.

Steam Steam

Liquid Liquid

High DR Low DR

Figure 5. High versus low distribution ratio

The V/L distribution ratio describes how much of the substance present in the steam
phase will condense with the condensate that forms or remain with the steam. The vapor:
liquid distribution ratio varies with pressure. For example, Table 11 gives the ratios for
carbon dioxide versus pressure.

Table 11. Distribution Ratio for CO2 versus Pressure

Pressure (psig) V/L ratio CO2

0 3.0
150 4.8
450 8.5
600 15.8
900 >99.0

25
If complete condensation of the steam occurs, then distribution ratio has little implication
since all the amine present will condense along with the steam. It is important to realize
that V/L ratios are only significant when a phase separation occurs. In the case of a flash
tank, condensate enters the vessel while both condensate and steam exit the vessel. Low
volatility amines will remain in the condensate while high volatility amines will flash
with the steam and exiting the tank.

For carbon dioxide to be neutralized, the amine must be present in the condensate as the
CO2 dissolves. For example, a V/L ratio of 4.0 indicates that 4.0 ppm of amine must be
present in the steam prior to condensation to achieve 1.0 ppm in the condensate. If
enough amine is not present in the steam, there will be insufficient amine to neutralize the
carbonic acid formed and a low pH in the condensate will result.

The distribution ratios of common amines used in condensate treatment are listed in
Table 12:

Table 12. Distribution Ratios for Common Amines

Amine V/L Ratio

Ammonia 10.0
Morpholine 0.4
CHA 4.0
DEAE 1.7
MOPA 1.0
DEHA 1.3

Thermal stability is the last characteristic that needs to be considered. In most industrial
boilers, most amines are stable and their use is not limited by boiler pressure. However,
DEAE will begin to breakdown at 1000 psig. This issue has its biggest impact on utility
operations where the combination of high pressure and superheater outlet temperatures
will cause many amines to degrade to ammonia and organic components.

The preferred application point for neutralizing amines is to the main steam header.
Feeding amine to the deaerator will result in losses through the vent while injection to the
feedwater will result in product loss through the boiler blowdown. All amines will suffer
some loss in the boiler blowdown if the products are added to the feedwater or to the
boiler itself. The amount of a specific amine lost will vary according to its V/L ratio as
well as boiler pressure, cycles of concentration and azeotrope information. There are
cases such as in high purity feedwaters where application of amine for feedwater pH
adjustment is required.

26
Filmers Filmers are organic materials that form a thin, non-wettable layer on all metal
surfaces coming in contact with the condensate. This film acts as a barrier between the
metal surface and the condensate, protecting the metal from corrosive species in the water.
Filmers protect against both carbonic acid and oxygen attack; a filmer program does not
neutralize CO2 as do neutralizing programs. Filmers find their greatest utility in
condensate systems where oxygen levels are high.

Most of the common filmers are long chained hydrocarbon molecules with a terminal
amine group. This amine group gives the molecule a hydrophobic (water-hating) end
while the other end is hydrophilic (water-loving). The hydrophobic end adsorbs on the
metal surface while the hydrophilic, long-chained end projects away from the metal
surface and into the water phase. This is depicted on Figure 6. With adequate feed rate,
a continuous monomolecular film is established. Overtime, the density of the film
increases but its thickness remains the same.

Figure 6. Orientation of Filmer on Condensate Surface

The protective film is generally quite stable to environmental conditions. However, the
film is not permanent and is in equilibrium with the water. A constant feed of excess
filmer is needed to maintain the integrity of the film. If feed of filmer is interrupted, the
film will gradually be lost. Amine films are pH sensitive, with condensate pH being
regulated in a range between 6.5 and 8.5 for greatest protection. Depending on the CO2
load, the neutralizing amine formulated with the filmer may be sufficient to maintain the
pH in this range. If not, a supplemental feed of a neutralizing amine may be required. If
proper pH is not maintained, the film will strip and leave a super clean surface that will
be very susceptible to corrosion.

It is important that filmers not be overfed. Filming amines are prone to forming a stick
deposit or “gunk balls” when fed in excess. These deposits can cause pluggage in steam
traps, pump strainers, control valves and other low flow areas of a system. Where boiler
carryover is an issue, the resulting high pH and high TDS of the condensate will interfere
with optimal filming and can lead to gunking.

Filmers are essentially surfactants and have significant detergency action. Care should be
taken when starting up a filming program in a previously untreated system due to system
clean-up and the transport of old deposits. Initial dosages should be low and slowly
increased in a step-wise fashion after condensate iron levels have stabilized.

27
Octadecylamine (ODA) is a commonly used straight chained filming amine with FDA
approval for use in steam that comes in contact with food. Soya- and tallow-based
amines are branched making them more soluble and thus have a lower tendency for form
deposits, but do not have FDA clearance. The newer, non-amine filmers not only have
some the performance advantages of these amine filmers but are acceptable for use in
food and dairy plants.

One economic advantage of filmers lies in the fact that their feed rate is solely based on
the metal surface demand for filmer and does not depend on the level of CO2 in the
system. Where CO2 is high, a combination filmer/neutralizer program may provide
improved cost performance over a straight neutralizing amine. In addition, filmers can
enhance heat transfer by improving heating surface cleanliness and promoting dropwise
condensation that reduces water film formation that lowers heat transfer.

Filmers should be fed to the main steam header since they are not volatile. An injection
quill is needed to insure proper dispersion of the filmer into the steam flow. Typical feed
rate is between 1 and 5 ppm of active filmer depending on the filmer chemistry being
used. Filmers must be dosed continuously with a slight residual in the return so that film
integrity is maintained. Filmers should never be used where turbines are present in the
steam cycle.

Volatile Oxygen Scavengers (VOS) Volatile oxygen scavengers represent a third type
of chemistry that can be used to treat condensate systems. The most common of these is
DEHA. DEHA is an amine with mid-range volatility (DR=1.26) and low basicity. When
combined with neutralizing amine, DEHA can protect against both carbon dioxide and
oxygen attack. It has strong passivation action, converting both iron and copper to more
reduced, stable stages that are more resistant to corrosion. Because of its volatility,
DEHA can be fed like a neutralizing amine. For best results, an excess of DEHA in the
return condensate will result in the lowest possible iron levels. In some cases, total amine
fed to the system can be reduced without sacrificing protection. DEHA can not be used
in steam that contacts food.

Monitoring The selection and application of a condensate treatment program will be

most successful when all aspects of the system metallurgy, design and operation are
considered. A detailed survey is the first step in understanding the requirements of the
system. An improperly selected or incorrectly applied treatment program will not result
in complete protection of the condensate system.

Monitoring the pH of the condensate is the most critical aspect to insuring proper system
protection. It is important that not just the bulk condensate at the boiler house be tested,
but condensate from all areas of plant be checked. This is because the distribution of
CO2 and O2 as well as amine is not uniform thorough the system. It is common to find
areas where the pH is below its recommended range even though the main condensate is
within limits.

28
In addition to pH, testing of conductivity, alkalinity and hardness provide information on
overall condensate quality. Both iron and copper should be tested as well to determine
the level of corrosion product present. This is the best indication of how well the
program is working. The best method for monitoring iron is the use of 0.45 um
membrane filters. A fixed volume of condensate is passed through the filter which
removes particulate iron that is present. The color and intensity of the filtrate residue is
compared to standard charts like the one in Figure 7 to determine how much iron is
present. The filter pads can be archived to track and document the level of corrosion
product over time.

Figure 7. Example of a Membrane Filter Comparison Chart

29
Buckman Asia Pacific boiler product lists are as seen on Table 13 below:

Table 13. Buckman Boiler Treatment Products

!"# #" $ " $ # % $&

#% $ $ $ '"& & ("

$% & ' ( ) * # (
! " # + ,, #
$% & ' ( + ) * #
! $ - % ( ,, #
$% & ' ( + ) * #
- % ( !+ , , #
. - / +
. - 0 #
$% !( )* # %
. 1& 2 ,3 ( +! , , #
. 2 ,3 0 4' 5 !(0 6) +
. . 2 ,3 '7 ! (0
$% !(! )* # %
.!! 2 ,3 & 8 9 , 8 9 ( + ,, #
1 9 #
& # / 0 * :!+ + !
1 9 #
! & # / 0 * :!+ + !
1 9 #
& # / 0 * :!+ + !
1 9 #
& # / 0* : + + !

30
Buckman Treatment Guidelines – Reverse Osmosis

Filtration is a commonly used process for the removal of suspended particulate solids
from water. Under the best of circumstances, traditional filtration techniques can remove
particle sizes down to only one micron. The membrane-based technologies of
microfiltration, ultrafiltration, nanofiltration, and reverse osmosis processes were
developed to remove specified ranges of particles and in some cases materials of
molecular and ionic size. The range of particle sizes is shown in Figure 8. The following
discussion will focus on the process of reverse osmosis.

Figure 8. Spectrum of Particle Filtration

THE PROCESS OF OSMOSIS

Osmosis is the process where a solvent (usually water) passes from a dilute solution into
a more concentrated one by moving through a semi-permeable membrane. This
membrane selectively allows the passage of the solvent, but restricts the passage of the
solute (dissolved solids).

The process of osmosis is demonstrated in Figure 9. It depicts a U tube with a semi-

permeable membrane separating two solutions with different levels of dissolved solids.
Over time, osmosis will occur, changing both the level of water and level of dissolved
solids on each side of the U tube. At equilibrium time, all of the forces or pressures
affecting osmosis will balance and the passage of water will stop. In actuality, the flow
of water through the membrane doesn’t really stop; it is just equal in both directions.

31
Figure 9. Illustration of Osmotic Pressure

Figure 9. Illustration of Osmotic Pressure

<1000
1000 ppm
ppm Pure
Water Pure
NaCl NaCl Water
Time = Zero Equilibrium Time

There are a number of different pressures involved in osmosis. The first is the osmotic
pressure, which is a function of the amount of dissolved solids in the water. In the above
example, assume (at time zero) that the solution on one side contains 1000 ppm of
dissolved solids while the other side is pure water or 0 ppm dissolved solids. For every
100 ppm differential in dissolved solids, there is one psi of pressure created. Therefore,
the difference of 1000 ppm of dissolved solids will create 10 psi of net osmotic pressure.
Since pure water travels through the membrane to dilute the more concentrated solution,
the osmotic pressure of 10 psi is in the direction of the more concentrated solution.
When the net osmotic pressure becomes zero, the flow across the membrane has reached
equilibrium.

The second pressure is the applied pressure, of which there are two types. The first is the
hydrostatic or head pressure, which is the amount of pressure generated by the height (or
weight) of water in a water column. One psi of head pressure is created by 2.3 feet of
water height. The second is external pressure or the pressure applied by some other
outside source. In most cases, it is generated by the high pressure feedwater pump.

The summation of all these pressures is the net driving pressure (NDP). This is the net
pressure on the surface of the membrane that causes water to pass through the membrane.
If the net driving pressure is zero, there is no net flow of water through the membrane.

REVERSE OSMOSIS

When sufficient external pressure is applied to overcome the osmotic pressure and
hydrostatic pressure on the membrane, the net driving pressure becomes positive and the
flow of water across the membrane is reversed. Under these conditions, reverse osmosis
takes place, which causes water to flow from the more concentrated solution to the dilute
one.

In simple filtration, there is one flow in and one flow out; all the water entering the filter
passes through the filtration media where suspended solids are filtered out and the water

32
exits as filtrate. In reverse osmosis, there are actually three different water flows (one
flow in and two flows out) as shown in Figure 10. This is why reverse osmosis and
similar processes are referred to as cross-flow filtration.

Figure 10. RO Unit Flows

Permeate
Feedwater

Concentrate

The three flows are:

• Feedwater entering the unit.

• Pure water flowing through the membrane. This flow is referred to as permeate
or product.

• Feedwater exiting the unit that has not passed through the membrane. This flow
is referred to as concentrate or reject. Since the permeate is relatively pure water,
the dissolved solids or salts left behind concentrate in the reject waste stream.

With this understanding of the flows in a reverse osmosis system, the net driving pressure
can be expressed as the feedwater pressure being supplied by the high pressure pump,
plus the osmotic pressure of the permeate, minus the permeate or system back pressure
and minus the osmotic pressure of the feedwater (see Figure 11).

NDP = Feedwater Pressure + Permeate Osmotic Pressure – (System Back Pressure +

Feedwater Osmotic Pressure)
Figure 11. Net Driving Pressure

3
4
1
2

(1) Feedwater Pressure + (3) Osmotic Pressure of Permeate

– (4) Permeate Back Pressure – (2) Osmotic Pressure of Feedwater

33
Process Performance One parameter used to measure membrane performance is salt
rejection, which refers to the dissolved solids that were present in the feedwater but did
not pass through the membrane and were retained in the concentrate. The percent salt
rejection can be calculated using the following equation:

TDS Feedwater - TDS Permeate x 100

TDS Feedwater

If the feedwater contains 100 ppm TDS and the permeate contains 5 ppm, then the
percent salt rejection is 95%.

Another membrane performance measurement is percent recovery, which is the

percentage of the feedwater that has passed through the membrane and is recovered as
permeate or product water. Percent recovery can be calculated using the following
equation:

GPM Permeate x 100

GPM Feedwater

If the feedwater flow is 100 gpm and the permeate flow is 75 gpm (therefore the reject
flow is 25 gpm), then the percent recovery is 75%.

Since the solids in the feedwater do not pass through the membrane, the solids build up or
cycle in the concentrate. This is analogous to a cooling tower where evaporation causes
dissolved solids to cycle up in the recirculating water. One can determine how many
times the concentrate has cycled by simply dividing the feedwater flow by the
concentrate flow. In the above example, the unit has cycled 4 times.

Membrane Configurations There are three basic membrane configurations commonly

used in water treatment:

1) Tubular In this configuration, the membranes are shaped like tubes inside a
supporting shell. Typically feedwater enters the inside of the tube and permeate collects
on the outside within the shell. The membrane tubes can be as large as ½ to one inch in
diameter.

2) Hollow Fiber With hollow fiber membranes, the geometry allows a high
membrane surface area to be contained in a compact module. Hollow fiber membranes
have diameters below 0.1 µm and are therefore very susceptible to plugging. While used
to produce potable water, hollow fiber membranes find their greatest utility in food and
pharmaceutical purification applications.

3) Spiral Wound This is the configuration that is most prevalent in water treatment
applications. The term “spiral wound” comes from the fact that the membrane is a flat
sheet that is rolled into a membrane element.

34
There are two types of membranes used in spiral wound construction. They are known as
cellulose acetate and thin film composite due to their materials of construction. While
both types are cast on the same kind of backing material, other aspects of their
construction differ.

With cellulose acetate membranes, the porous support and salt rejection layer (dense skin)
are made of cellulose acetate blends. The salt rejection layer has a smaller pore size than
the support layer. Thin film composites have different components for the porous
support and semi-permeable membrane, which actually rejects salt. The thickness of the
semi-permeable membrane is about half the thickness of the dense skin on the cellulose
acetate membranes. The structures of these membrane types are shown in Figure 12.

Figure 12. Structures of Cellulose Acetate and Thin Film Membrane Types

Dense Skin
Porous Support
Backing Material

Cellulose Acetate Membrane Thin Film Composite

A comparison of these membrane types is found in Table 13.

Table 13. Comparison of Cellulose Acetate and Thin Film Composite Membranes

Parameter Cellulose Acetate Thin Film

Cost More expensive Less expensive
Typical Salt Rejection 96 % 97 - 98.5 %
Operating Pressure Up to 700 PSI Up to 275 PSI
pH Range 4.8 - 6.5 2 - 10
Chlorine Tolerance Good Very low
Compaction Tendency More Less

35
With cellulose acetate membranes, operating pH is critical to maintain membrane
integrity and life expectancy. Hydrolysis of the acetate is significantly higher outside its
recommended range. Conversely, it is much more stable with respect to the presence of
oxidizing agents in the feedwater. Chloramines can be used with thin film membranes
with minimal impact on their service life.

Element Construction A cross section of a spiral wound membrane can be seen in

Figure 13. A perforated tube runs down the center of the membrane element. This is
called the permeate tube because it is the channel by which permeate leaves the element.
A sheet of membrane “envelope’ along with a feedwater spacer is wound around the tube.
The spacer is a plastic screen that provides turbulence as the feedwater passes over the
surface of the membrane sheet. The envelope consists of two pieces of flat sheet
membrane with a permeate carrier between them. Three sides of the envelope are glued
together so that when pure water flows through the membrane, it only has one exit as it
travels along the carrier and into the permeate tube. Within an element, 20 to 25
envelopes may be wrapped around a single permeate tube.

Figure 13. Cut-away of a Spiral Wound Membrane

Permeate Collection Tube

Concentrate Out
Feedwater In
Permeate Out
Feedwater In Concentrate Out

Feedwater Flow
Across Channel
Spacer

Permeate Flow

After the element has been rolled and taped, the ends are precisely cut through the glue
lines so that the envelope remains sealed. End caps (called anti-telescoping devices) to
keep the envelopes in place are attached, decals and colored identification stripes are
applied, and the assembly is covered with an outer layer of fiberglass. Each element is
then pressure tested, preserved by soaking in a sodium metabisulfite solution, and then
stored for shipping.

RO Unit Designs A series of elements are joined together at the permeate tubes by
inter-connectors into a single pressure vessel. A pressure vessel with four spiral wound
elements is showed in Figure 14, although a larger number of elements are typically used.
These pressure vessels are combined to create an RO unit. These units can be configured

36
in a number of different ways depending upon the desired overall recovery, salt rejection
desired, and volume of permeate required.

Figure 14. Diagram of a Pressure Vessel

End Cap Adaptor Inter-connector Permeate Tube

Element Element Element Element

End Cap Brine seal

Figure 15 shows a single pass, single stage reverse osmosis unit with a 50% recovery.
The term “single pass” refers to the fact that the feedwater makes only one pass across
the unit. “Single stage” means that there is only one stage and the concentrate does not
become feedwater for a second set of pressure vessels. In this case, the stage has 4
pressure vessels into which the feedwater is being split. “Fifty percent recovery”
indicates that half of the feedwater is being recovered as permeate with the balance being
wasted as concentrate.

Figure 15. Single Stage Reverse Osmosis Unit

Permeate
50 gpm

Feedwater
100 gpm

Concentrate
50 gpm

37
Figure 16 depicts a single pass, two stage reverse osmosis unit with a 75% recovery.
Once again, single pass means that the feedwater makes only one pass across the unit.
With two stages, the concentrate from the first stage serves as feedwater for the second
stage. The figure shows that feedwater is split into 4 pressure vessels, and the reject from
these enters the two pressure vessels in the second stage. This configuration is referred to
as a 4 - 2 array. A recovery of 75% means that the total amount of permeate generated
across both stages is ¾ of the initial feedwater and the balance is rejected as concentrate.

Figure 16. Two Stage, Single Pass Reverse Osmosis Unit

1st Stage Permeate

50 gpm Combined
Permeate
75 gpm

Feedwater 2nd Stage

100 gpm Permeate
25 gpm

1st Stage Combined

Reject Reject
50 gpm 25 gpm
1st Stage 2nd Stage

A single stage, two pass reverse osmosis unit with 25% recovery is illustrated in Figure
17. It is two pass because the initial feedwater passes across the units twice—in the first
as the original feedwater and in the second as permeate from the first. It is single stage
since the concentrate from both passes is not processed further. The recovery from this
unit is only 25% since only one quarter of the original feedwater is recovered as permeate.

38
 Figure 17. Single Stage, Two Pass Reverse Osmosis System

1st Pass Permeate 2nd Pass Permeate

25 gpm 25 gpm

Feedwater
100 gpm

2nd Pass Reject

25 gpm

1st Pass Reject

50 gpm

WATER TREATMENT CONSIDERATIONS

From a water quality perspective, there are three areas of concern. These are fouling,
scale formation, and microbiological fouling. Fouling is a concern since the RO
membrane is an excellent filter and can physically plug due to particulate in the feedwater.
The same phenomenon that causes scale formation in a cooling tower or boiler can lead
to deposition in the RO. When dissolved solids in the concentrate become too high, the
solubility of various salts can be exceeded and their precipitation from the bulk water
onto the membrane surface results. The RO membrane is also an ideal environment for
the growth of microorganisms, which can proliferate at a rapid rate and cause flow
through the membrane to be impeded.

Fouling by Suspended Solids Suspended and colloidal solids in the feedwater will
accumulate on the membrane surface. The fouling tendency of a feedwater is measured
using a parameter called the silt density index (SDI). The SDI is determined by
comparing the time required to filter 500 ml of feedwater through a 0.45 m filter at the
beginning of the test and after 15 minutes of continuous filtration. The SDI is much more
sensitive than turbidity in predicting the fouling potential of a feedwater. If the SDI is
greater than 5, most manufacturers agree that the water is not suitable for use without
further pretreatment. Often a multimedia filter is installed to improve feedwater quality.
Regardless of the SDI, all RO systems will have a cartridge filter (usually 5 m) before
the membranes.

Scale Formation The formation of scale in the membrane is the result of the
concentration effects as dissolved solids build up in the concentrate. While fouling will

39
usually manifest itself in the first stage, scale generally begins in the second stage of an
RO unit (or perhaps in the last several elements of a single stage unit).

When scaling occurs, a number of operational symptoms can be observed. These include:

• Decrease in permeate quality reflected in increased permeate conductivity

• Dissolved solids in the concentrate, which will be lowered due to precipitation
• Decrease in permeate flow due to the physical blockage of flow across the
membrane

• Increase in the pressure difference ( P) in the final stage or array

There are a number of approaches that can be taken to eliminate or control scaling:

• Feedwater quality can be improved by pretreating the water to reduce or eliminate

the scale-forming species. For example, a water softener can be placed ahead of
the RO to remove scale-forming hardness from the water.
• Acid can be fed to lower pH, thereby increasing the solubility of scale-forming
salts. This method is often used for the control of calcium carbonate scale.

• Scale inhibitors can be applied to the feedwater ahead of the membranes. These
may include phosphonates, dispersants, or combinations thereof depending upon
the nature of the scale.

Microbiological Fouling The fouling of RO units due to microbiological growth is a

common problem. This is due to the fact that microorganisms are ubiquitous and
constantly inoculate the system. The environmental conditions of pH and temperature
are typically ideal to support the growth of microbial populations. The rough surfaces in
the RO such as feedwater and permeate spacers provide excellent locations for the
proliferation of microbes. Lastly, the constant flow of feedwater brings a continuous
supply of nutrients to support growth.

The presence of excessive microbiological growth can be seen in a number of ways:

• Presence of slime in pretreatment equipment

• Characteristic biological odor

• Slow, steady increase in feedwater pressure

• Slow, steady increase in 1st stage/1st array P

• Reduced permeate flow

The last three symptoms can also indicate colloidal fouling of the membrane.

40
Microbiological fouling can be controlled using a number of different methods:

• Maintain a chlorine residual throughout pretreatment equipment.

• If possible, get rid of activated carbon units.

• Intermittent feed of a nonoxidizing biocide; in extreme cases, continuous low
level feed can be used.
• Alternate biocides for full spectrum coverage.

• Thoroughly clean and sanitize the membranes in accordance with the
manufacturer’s recommendations.

Some clarification on the use of activated carbon is warranted. The units are a notorious
breeding ground for microbiological activity. Activated carbon beds are included in
many RO units for two reasons: (1) the removal of residual chlorine before the
membrane and (2) organic removal. Thin film composite membranes are typically
guaranteed for only 1000 ppm-hours of residual free chlorine exposure. Chlorine
removal can be readily accomplished using sodium metabisulfite to get rid of the chlorine.
However, removal of the carbon units can result in higher TOC, which could be more
detrimental than a microbiological problem.

Chemical Cleaning Almost all RO units need to be chemically cleaned periodically

to restore the operating effectiveness of the system. The type of chemistry used in the
cleaning is dependent on the nature of the foulant to be removed. Acids are generally
used to clean scale since most salts can be resolubilized by low pH. Caustic or alkaline
cleaners are used primarily for organics and microbiological foulants. Chelants such as
citric acid are used when iron is involved. They also help in acidic situations when
cleaning scale. Proprietary formulations can provide enhanced cleaning performance
because they are formulated with multiple ingredients that include the aforementioned
along with dispersants, surfactants, and enzymes when appropriate.

Most systems include an external cleaning skid for recirculation of cleaning solutions
through the pressure vessels. A typical cleaning skid is shown in Figure 18.

41
 Figure 18. Chemical Cleaning Skid

The following components should be included in all cleaning systems:

• A cartridge filter to remove suspended solids, which will prevent redeposition of

removed contaminants onto the membranes

• A sample point to allow monitoring of pH and other cleaning solution parameters

• A flow indicator and control valve to adjust flow rate to recommended levels
• A heating element along with controller and indicator to maintain the cleaning
solution at the recommended temperature

• A cleaning tank large enough to contain 2.5 to 3 times the volume of the first
stage and associated piping
• An acceptable mixing system to properly disperse the cleaning chemicals

• A recirculating pump that can deliver up to 1.5 times the normal concentrate flow
at low pressure

• Pressure gauges to monitor differential pressure across the vessels

There are a number of rules that a successful chemical cleaning must follow. These
include:

• The chemical cleaning solution should be made up at the proper strength.

• Chlorine-free deionized water or permeate should be used as dilution water for the
cleaning solution.
• Water in the pressure vessels should be completely displaced with cleaning
solution or water of permeate quality or better before the cleaning is started.

• Each stage should be cleaned separately.

42
 • The combination of high velocity flow rates at low pressure should be used during
the cleaning.
• The cleaning solution should be kept at the recommended temperature throughout
the cleaning cycle; exceeding the manufacturer’s recommendations will void the
membrane warranty.

• When following both acid and alkaline cleaning steps, the low pH cleaning should
be done before the high pH one.
• The composition of the cleaning solution should be based on the contaminants
that need to be removed.

• Sufficient time should be allowed to insure that the cleaning has been effective.

• At no time should the pressure differential during cleaning exceed 10 psi per
element in a pressure vessel.

MONITORING AND TROUBLESHOOTING

In addition to basic flows, pressures, and water chemistry, the following parameters
should be recorded and trended over time to determine how the RO system is performing.
This information can be used to determine when the unit should be cleaned and to
troubleshoot performance issues as they arise.

Normalized permeate flow (NPF) compares current RO performance with what it was
when the unit was new. It accounts for changes in permeate flow rates, temperature,
feedwater salt concentrations, and operating pressures when making the comparison.

The normalized permeate flow is calculated using the following equation:

NPF = (NDPstartup/NDPcurrent) x TCF x GPMpermeate

where
NPF = normalized permeate flow in gpm
NDPstartup = net driving pressure with new unit
NDPcurrent = net driving pressure under present conditions
TCF = temperature correction factor
GPMpermeate = current flow rate of permeate

The NPF should be monitored over time. If it drops by more than 10%, the unit is fouled
to the point where it should be chemically cleaned.

Differential pressure ( P) is the difference in the pressure of the feedwater entering and
the concentrate leaving the pressure vessel. If the P increases by more than 15%, the
pressure vessel requires chemical cleaning. It is important to remember that the P
should not exceed 10 psi per element in the pressure vessel or physical damage to the
elements will result.

43
Percent salt rejection is the ratio of TDS of the permeate versus that in the feedwater. If
the conductivity of the feedwater is 160 µmhos and that of the permeate is 8 µmhos, the
salt rejection for the unit is 95%.

Percent recovery is the ratio between gallons of permeate generated versus the feedwater
flow expressed as a percent. If feedwater flow is 100 gpm and permeate flow is 75 gpm,
the percent recovery is 75%.

If these parameters indicate a performance issue with the RO, the following items should
be checked to troubleshoot the problem:

SDI of the feedwater should be checked periodically to insure that its quality has not
deteriorated over time. An SDI greater than 5 will definitely cause a fouling problem in
the membranes, but values lower than this can also be problematic depending on the
nature of the turbidity. If the SDI trend is increasing, additional pretreatment equipment
may be warranted.

Profiling is a procedure where the conductivity or TDS of the permeate exiting each
pressure vessel is measured and compared to past readings. This permits identification of
the pressure vessel at fault when the overall quality of permeate from an RO unit
deteriorates.

Probing is used to determine the permeate quality at different locations within a single
pressure vessel. The probing tool is a tube that has been pre-marked based on the
specific location of the elements and O-rings within the pressure vessel. The tube is
inserted down the entire length of the pressure vessel. Permeate samples are measured at
the marked intervals as the tube is being withdrawn to identify the exact spot where
permeate quality is poor.

Cleaning solution sampling can provide valuable insight into the effectiveness of
chemical cleaning as well as the nature of the foulants being removed. The presence of
inorganic and organic contaminants can be confirmed by laboratory analysis.

Membrane autopsy is a destructive testing method where the element’s fiberglass shell is
cut away and the internal components are inspected. Visual observation can detect
physical problems such as mechanical damage and membrane fouling. Laboratory
analysis and microscopic examination of deposits that are present can yield valuable
information as to the nature of the problem. The structure of the membrane can also be
examined to determine whether any deterioration of the membrane itself has occurred.

44
 Buckman RO Products Selection Chart

Single Component Product

Scale Inhibitor Only Yes No FDA 176.170? Yes

Yes No No Bulab 8830

Bulab 8802 Combination Scale Inhibitor / Dispersant? Primary Scaling / Fouling Species

Yes No Silt? Iron? Silica?

Bulab 8808
Order of Scale Inhibition Importance Dead End

1-5, 1 Being 1-5, 1 Being

Best Best
1) Sulfates 1) Carbonates 1) Bulab 8805 1) Bulab 8807
2) Carbonates 2) Sulfates 2) Bulab 8806 2) Bulab 8808
3) Bulab 8830 3) Bulab 8806
4) Bulab 8807 4) Bulab 8830
5) Bulab 8808 5) Bulab 8805
Bulab 8803 Bulab 8804

Carbonates and Sulfates?

Primary Scaling Species?

Sulfates Carbonates

1-5, 1 Being 1-5, 1 Being

Best Best
1) Bulab 8830 1) Bulab 8806
2) Bulab 8806 2) Bulab 8805
3) Bulab 8805 3) Bulab 8830
4) Bulab 8807 4) Bulab 8807
5) Bulab 8808 5) Bulab 8808

45
Buckman Treatment Guidelines – Cooling Water
Organic Treatment

Background

Organic programs have developed to the point that they can be applied in most commonly
encountered waters. The combination of low environmental impact and good corrosion
protection has made this technology the most widely used of any program. The main
drawback of using an organic program is that in “hot” systems, particularly heat exchangers
(outlet water temperature > 60°C), the high alkalinities that are used, make it difficult to
control scaling rates.

Corrosion Inhibition
This type of program inhibits corrosion via four main routes:

Calcium carbonate film formation.

Calcium phosphonate film formation.
Chemisorbed film.
Relying on lower corrosivity of alkaline water.

As we discussed in the section on corrosion, one route to lowering corrosion rates, is to form
barrier films to inhibit the diffusion of oxygen to the metal, and ferrous ions from getting
away.

Under the conditions used for all organic programs, the water is scale forming and without
phosphonates and polymers, rapid scaling will occur. The soluble calcium bicarbonate
changes when heated, to give:

heat
Ca(HCO3)2 CaCO3 + H2O + CO2

The purpose of the anti-scalants is not to prevent all calcium carbonate formation, but to
keep it at acceptable levels. In effect, to allow just enough calcium carbonate to form to stop
the corrosion, but not enough to impede heat transfer.

Besides acting to control calcium carbonate, phosphonates also serve to act as corrosion
inhibitors in their own right. Phosphonates can react with either calcium or iron ions and
precipitate out at corrosion sites.

Both of these reactions require alkaline conditions to allow the reaction to go to a

reasonable level of completion. To enhance corrosion control, specific materials are used
which bond onto the copper, and form a chemisorbed film. These chemicals typically
contain nitrogen or sulphur atoms, which take part in the bonding process.

46
Scale Control

Scale control actually involves preventing excessive scaling under conditions that favour it.
Besides adjusting the hardness level via bleed-off and controlling the alkalinity either with
acid or bleed-off, two other methods are used.
Phosphonates and anionic polymers are used to:

Disperse suspended solids.

Modify crystal structure of scale.

Inhibit the formation of scale.

Even with these chemicals, some control over the hardness and alkalinity levels of the
water is necessary. Bleed-off can be used to keep the hardness level below a maximum
value. In some cases, this is sufficient to also control the alkalinity/pH.

However, if the alkalinity is still too high, or if more cycles of concentration are required,
acid may be used. The reaction of an acid, typically sulphuric acid is:

H2SO4 + CaCO3 CaSO4 + CO2( ) + H2O

Other acids can be used, but sulphuric acid offers the advantages of low cost, ready
availability, and the sulphate anion is not especially corrosive. Generally, hydrochloric acid
is not used, since excessive chloride levels can increase the corrosivity of the water.

Control Limits

These vary a great deal, due to the differences in local water conditions and water quality.
Furthermore, the type of product being used, and the specific plant conditions, can play a
large role in the limits set.

A general rule is that the cooling water must be alkaline (pH above 8.3), and typically, at
least 150 ppm of ' M'alkalinity should be present. With only a few exceptions, the ' M'
alkalinity must be less than 400 ppm to prevent loss of calcium due to scaling.

The total hardness should also be kept above 150 ppm in the cooling water, and for best
results, a more normal value is above 400 ppm. An upper limit cannot be set, since it is a
function of alkalinity, plant conditions, and product selection.

47
 Product Selection
Depending on the circumstances, heavy industrial clients are normally dealt with on a site
specific basis. Large plants may have a variety of unique problems that require attention,
such as:

High heat flux rates.

Low flow areas.
Unusual water quality.
A typical system metallurgy.

Organic Treatment Program Selection Chart

High High
Scaling Bulab 9338*
Corrosivity
Tendency

Low
Low
Bulab 9328
Bulab 9083**
Bulab 9132***
Scaling
Tendency Bulab 9373*
High
Bulab 3725

Low * No copper protection. Add 9027 if needed

** Molybdate blend. For mild steel pitting corrosion inhibitor
Bulab 9342 *** Pyrophosphate blend. For Iron sequestrant and mild steel corrosion inhibitor
Bulab 9327

Typical
Product Main Component Dosage, Application Criteria Remark
ppm
1 Drum Scale and Corrosion
Bulab 9328 PO4/Organic/Copol/Azole 60 – 120
Inhibitor
1 Drum Scale and Corrosion
Bulab 9338 PO4/Organic/Copol 60 – 120
Inhibitor
Bulab 9083 MoO4 15 – 75 Molybdate Source
Bulab 9132 Polyphosphate 20 – 40 Poly-PO4 source
Bulab 9373 Organic/Copol 60 – 120 1 Drum All Organic
Bulab 3725 Organic/Copol/Azole 60 – 120 1Drum All Organic with Azole
Bulab 9342 Organic/Copol/Azole 50 – 150 1 drum All Organic with Azole
Bulab 9327 Organic/Copol/Azole 60 – 120 1 Drum All Organic with Azole

48
High (Stabilized) Phosphate

Background
For several decades it was known, that inorganic phosphates were capable of corrosion
control, both by passivation, and barrier film formation. The levels of phosphate required to
give good corrosion control were too high to be tolerated in most systems, without excessive
bleed-off, to control calcium levels. This made them not cost-effective.

With the development of polymers that allowed reasonable levels of phosphate and calcium
to co-exist, these programs became popular. Since they rely on controlled deposition of
phosphate, they are inherently scaling, although corrosion control is very good.

Corrosion Control
Phosphate programs rely primarily on the controlled deposition of calcium poly-phosphate
at the cathode, and iron phosphate at the anode. While this is the main form of corrosion
control, other inhibitors are also used.

Polyphosphates are typically used to act as cathodic inhibitors, so as to reduce the risk of
pitting corrosion, should the orthophosphate levels drop below the minimum value required.
Due to hydrolysis, some of the polyphosphate will revert to orthophosphate. Azoles are also
included to improve the corrosion inhibition on copper and copper alloys.

Since these programs are operated under neutral pH conditions, no significant formation of
calcium carbonate is likely to occur, except during upsets.

Scale Control
Since phosphate programs are inherently scaling, this area is one of major concern. Anionic
dispersants (polymers) are used to inhibit calcium phosphate formation under conditions
which would normally favour it. If the polymer feed is lost, rapid scaling can be expected to
take place.

The polymers work both by inhibiting the initial precipitation of calcium phosphate, as well
as distorting any crystals that form. The modification of calcium phosphate crystals that do
form serves to prevent them from acting as seeds, or growth sites, for further precipitation.

Phosphonates are also used, but their role is secondary to the part polymers play.
Phosphonates having only limited effectiveness against calcium phosphate are included to
improve control of iron and calcium sulphate deposits.

Control Limits
Since the operating control ranges for these programs are fairly restrictive, the control limits
do not show a lot of variation.

The pH range is kept between 7.0 to 7.5 using acid feed, and the total hardness is generally
less than 800 ppm. The phosphate range shows somewhat more latitude, depending on the
hardness in the cooling water, but one can list it as being between 10 - 17 ppm as PO4.

49
Since these programs can be negatively impacted by a number of factors, one should be
aware of them and develop contingency plans for them on a site specific basis. A number of
the significant ones are listed in the figure below:

Significant System Stressor for CWT Programs

System Stressors
Stressor Threshold Value For Each Additional Active
Polymer*
Soluble iron > 2 ppm 1 ppm 2 - 3 ppm
Temperature > 38oC (100oF) 5.5oC (10oF) 2 - 4 ppm
High suspended solids >15 NTUs 15 NTUs 2 - 4 ppm
High aluminium > 1 ppm 1 ppm 2 - 4 ppm
Low exchanger flow velocity <0.6 m/sec (2 ft/sec) --- 4 - 6 ppm
High silica >170 ppm 5 ppm 2 - 3 ppm

*Polymer selection:
Bulab 7034 (primarily suspended solids, also good for stabilizing Zn, o-PO4 and poly-
PO4)
Bulab 7041 (high temperature and Calcium, excellent for Iron dispersants)

50
 Product Selection
The one drum stabilized phosphate programs have the advantage of simplicity of application.
All components needed for a sound protection program are contained in this product.
However, it requires “forgiving” conditions to be feasible. Critical exchanger conditions
should be favorable (higher flow rates, heat flux not extreme, low stressor level), and
moderate pH, temperature, flow water quality, etc. should be predictable. The control
needed for a one drum stabilized phosphate product is less flexible than for two drum
programs.

High Phosphate Selection Guide

No Long No
Stable Retention Stressed
Bulab 9132
Condition? Time System?

Yes Short Yes

Bulab 9126 Bulab 9124 Bulab 9357

Bulab 9125

Note: No copper protection. Add 9027 if needed

Typical
Product Main Component Dosage, Application Criteria Remark
ppm
Bulab 9124 Ortho/Poly/Copol 60 – 120 1 Drum stabilized PO4
Bulab 9125 Ortho/Poly/Copol 60 – 120 1 Drum stabilized PO4
Bulab 9126 Poly/Copol 40 – 120 1 Drum stabilized PO4
Bulab 9132 Polyphosphate 20 – 40 Poly-PO4 source
Bulab 9357 Ortho/Poly/Copol 30 – 70 1 Drum stabilized PO4

51
Low (Extended) Phosphate

Background
Bulab 9328 is an improved cooling water treatment that provides enhanced corrosion
control in corrosive waters. When used properly, there is much less potential for calcium
phosphate sludging, while at the same time providing excellent corrosion control is possible.

This technology operates with low to medium levels of inorganic phosphate (4-8 ppm o-PO4)
and relies upon the calcium salts of inorganic phosphate to act as cathodic inhibitors. The
technology is similar to a high (stabilized) phosphate program, except the programs are run
at, or slightly below the pHc, making the phosphate completely soluble. This solubility
makes these programs less susceptible to scale formation. Also, since they are run at higher
pH, the system has more buffering capacity, and in some cases acid feed can be avoided.

The advantage of this approach is that in waters where there is naturally occurring phosphate
(or because of addition to the potable water), one can use this phosphate to provide the basis
for a cooling water treatment program.

Corrosion Control
This type of program relies predominantly on calcium phosphate for corrosion inhibition
although, depending on the water characteristics, calcium carbonate can play a significant
role. In many ways this is a mixed program, that lies between organic and traditional high
phosphate approaches.

Scale Control
As for phosphate programs, scale inhibition is primarily a concern with respect to calcium
phosphate and for this reason the amount of sulphonated co-polymer present in these
programs is relatively high. This polymer is also effective at dispersing calcium carbonate,
silt and corrosion products.

52
Control Limits
The table below lists what would be considered normal control limits for this type of
treatment.

Low Phosphate Control Parameters

Low Phosphate Programs

Program Limits Program Guidelines
CaH o-PO4 Cl- SO4
Cond Heat Flux
pH Ppm as ppm as Ppm as ppm as Temp
µmhos KBTU/hr/ft2
CaCO3 PO4 NaCl SO4
<50oC
7.0 - 8.2 100-500 4–8 <200 <500 <3000 <15
122oF

Product Selection

This technology can be run in any system, but it performs best in light to medium duty
systems, or in high duty systems with good flow rates. It is also the technology of choice in
systems where the make up water contains inorganic phosphate, which can be cycled into 4
- 8 ppm o-PO4 in the recirculating water.

This technology would be recommended under the following circumstances:

Inorganic phosphate in the make-up water

Environmental restrictions on Zinc usage and/or high levels of phosphate
Insufficient calcium and alkalinity combination to run an organic program
The plant does not wish to acid feed, even though it can be used with acid

53
 Low Phosphate Program Selection Guide

Yes
Background PO4 at Bulab 9327
4 - 8 ppm? Bulab 9373*
Bulab 7173

No

No
Any background Bulab 9328
PO4 ?
Bulab 9338*
Bulab 7170
Yes

Bulab 7173
Bulab 9208
Bulab 9210*

* No copper protection. Add 9027 if needed

Typical
Product Main Component Dosage, Application Criteria Remark
ppm
Bulab 9327 Organic/Copol/Azole 60 – 120 1 Drum all organic
Bulab 9328 o-PO4/Organic/Copol/Azole 60 – 120 Scale and Corrosion Inhibitor
Bulab 9338 o-PO4/Organic/Copol 60 – 120 Scale and Corrosion Inhibitor
Bulab 7170 o-PO4/PCA+/Copol/Azole 100 – 150 Low P technology, PCA+ based
Bulab 7173 PCA+/Copol/Azole 100 – 150 Non P Technology, PCA+ based
Bulab 9208 PESA/Terpol/Azole 60 – 120 Non P Technology, PESA based
Bulab 9210 PESA/Terpol 60 – 120 Non P Technology, PESA based
Bulab 9373 Organic/Copol 60 – 120 1 Drum all organic

54
Zinc-Phosphate/Phosphonate

Background
The various zinc-based programs are centered around the desire to retain the advantages of a
metal based program – that is excellent corrosion protection across a broad range of water
chemistries and a tolerance to upsets. The improved performance of this type of program is
related to achieving a more uniform distribution of the zinc phosphate film. Use of zinc
specific phosphonates allows the amount of zinc used to be reduced while at the same time
the actual corrosion inhibitor film integrity is improved.

Corrosion Inhibition
Since these programs are generally run under neutral to slightly alkaline conditions, calcium
carbonate is not a significant contributor to the corrosion inhibition process.

This type of program inhibits corrosion by relying on three principal mechanisms:

precipitation of zinc phosphate

precipitation of calcium phosphate
chemisorbed film formation

With 4 - 8 mg/L of ortho phosphate (as PO4) in the cooling water, a pH around 8.0 will
generally result in conditions that favor the precipitation of both zinc and calcium phosphate.
Since the solubility limit for zinc phosphate is much less than for calcium phosphate, even
relatively low concentrations of zinc in the bulk cooling water will favor its formation.

Under the local conditions at the cathode the pH will be sufficiently high to result in
precipitation of both zinc phosphate and zinc hydroxide. In practice a zinc concentration,
based on product feed, of 1 - 4 mg/L (as Zn) is normally sufficient to ensure that this
reaction is favored. Phosphonates, in particular PBTC, are very effective at preventing zinc
precipitation under conditions where one would expect it to occur. When this phosphonate
is combined with phosphate dispersants, deposition control is easy to maintain.

Depending on the bulk water pH, calcium phosphate can also play a role inhibiting
corrosion as there typically is sufficient calcium in the cooling water to exceed its solubility
limit. Although ortho phosphate is the major corrosion inhibitor, phosphonates that are
present can also react either with zinc or calcium. These reactions tend to be less significant
since these materials are more soluble than either zinc or calcium phosphate.

Azole(s) are part of these programs in order to ensure that yellow metal corrosion rates are
sufficiently low. Also they aid by reacting with any soluble copper ions that are formed and
preventing them from plating onto steel and initiating galvanic corrosion.

55
 Scale Control
An advantage of zinc-phosphate programs is their pH range, 7.5 - 8.2. In this range the
tendency to form calcium carbonate scale is typically quite low, even at relatively high bulk
water calcium concentration. Depending on the make-up water quality, acid feed is
normally required, but there are areas where the natural alkalinity is low enough that acid is
not needed.

While calcium carbonate scaling is normally not a problem, the use of both phosphate and
zinc make this type of program "inherently fouling". Consequently, polymers are used to
control the potential for bulk water precipitation of zinc and calcium phosphate. The
objective being to have enough polymer present to stop bulk precipitation but, not a
sufficient amount to prevent precipitation of the inhibitors at cathodic sites, where local
conditions are more extreme.

A combination of sulphonated and carboxylate polymers are used to provide a broad

spectrum of activity against zinc and calcium salts, as well as the normal silt and dust that
finds its way into the cooling water.

Phosphonates are used, but their role in the treatment is not scale inhibition but rather
corrosion inhibition. Phosphonates are not effective zinc or calcium phosphate scale
inhibitors and since the pH is controlled at a level where there is not much carbonate present,
there is little potential for calcium carbonate formation.

Control Limits
Although the limits will vary dramatically depending on the water composition the
following general guidelines will apply:

Typical Control Ranges for Zinc Programs

Zinc Based
Program Guidelines
CaH Alk. Cl- SO4
Cond. Heat Flux
pH Ppm as ppm as ppm as ppm as Temp Metals
µmhos KBTU/hr/ft2
CaCO3 CaCO3 NaCl SO4
<55oC Ferrous
7.5-8.2 100-500 80-300 <200 <500 <3000 <50 kw/m3
131oF yellow

56
 Product Selection
Although we can supply a variety of zinc-phosphate based cooling water treatments,
depending on heat exchanger exit temperatures and the performance criteria, the actual
selection process involves more than just ordering from the product manual. The selection
diagram is meant to be a guide and you should discuss matters with your supervisor before
choosing any program.

Zinc Product Selection Guide

Yes
Bulab 9063*
CaH < 200 ppm?
& Bulab 7034

No

Yes
CaH > 200 ppm? SS loading Bulab 9333
high? & Bulab 8022
No

Yes No

No
SS Loading Bulab 9181*
high? & Bulab 8022

Yes
* No copper protection. Add 9027 if needed
Bulab 9333
& Bulab 8022

Note: If you want to use the

3 drum system, use: B9050/B9320/B8022

Typical
Product Main Component Dosage, Application Criteria Remark
ppm
Bulab 9333 Zn/o-PO4/Organic/Copol 40 – 80 1 Drum scale and corrosion inhibitor
Bulab 9181 Zn/o-PO4/Organic/Copol 40 – 80 1 Drum scale and corrosion inhibitor
Bulab 8022 Organic/Copol 10 – 20 CaSO4, Ca3(PO4)2/Zn/Silt/Fe
Bulab 9063 Zn/o-PO4 20 – 40 1 Drum scale and corrosion inhibitor
Bulab 7034 Copol 10 -20 Ca3(PO4)2/Zn/Silt/Fe
Bulab 9050 Zn 5 – 20 Zn source
Bulab 9320 o-PO4 source 10 - 100 o-PO4 source

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 Inorganic Dispersants

Typical
Product Main Component Dosage, Application Criteria Remark
ppm
Bulab 7034 Copol 1 -15 Ca3(PO4)2/Zn/Silt/Fe
Bulab 7041 Terpol 1 -15 Fe/Ca3(PO4)2/Zn/Silt
Bulab 8022 Organic/Copol 10 – 20 CaSO4, Ca3(PO4)2/Zn/Silt/Fe
Bulab 8023 Organic/Terpol 10 – 20 Fe,CaSO4, Ca3(PO4)2/Zn/Silt
Bulab 7119 Organic Source 10 – 100 Phosphonate source
Bulab 7088 Silica Dispersant 10 – 100 Silica scale inhibitor
BL-7065 Organic/Copol 10 – 40 CaCO3/CaSO4/Ca3(PO4)2/Zn
Bulab 7016 Organic Source 5 – 25 CaCO3/ Silt dispersant
Bulab 7020 Organic Source 20 – 100 Modest CaCO3/silt dispersant
Bulab 7005 Organic Source 1 -15 CaSO4/Silt/modest CaCO3

Organic Biodispersants

Typical
Product Main Component Dosage, Application Criteria Remark
ppm
Bulab 8002 Organic/DMAD 1 -15 Biodispersant & inorganic dispersant
Bulab 8006 SASE/DMAD 1 -15 Biodispersant & inorganic dispersant
Bulab 80007 DMAD 10 – 20 Biodispersant
Bulab 8012 Surfactant / DMAD 10 – 20 Biodispersant – Oily water
Bulab 8031 DMAD/Surfactant 10 – 100 Biodispersant
Bulab 8065 Aromatic Solvent/Surfactant 10 – 100 Dust/deposit/silt//filler cleaning

Closed Cooling System

Typical
Product Main Component Application Criteria Remark
Dosage, ppm
Bulab 9070 NaNO2 powder 500 - 5000 Closed CW system corrosion inhibitor
Bulab 9076 NaNO2/Silicate/Azole 6000 - 8000 Closed Cooling System with Aluminum
Bulab 9077 NaNO2 blend 5000 – 8000 Closed CW system corrosion inhibitor
Bulab 9078 MoO4/NaNO2/Azole 5000 – 8000 Closed CW system corrosion inhibitor
Bulab 9079 NaNO2 blend 2000 - 4000 Closed CW system corrosion inhibitor
Bulab 9157 MoO4/NaNO2/Azole 5000 - 8000 Closed CW system corrosion inhibitor
Bulab 9189 NaNO2/Azole 5000 - 8000 Closed CW system corrosion inhibitor
Bulab 9546 MoO4/Amine 5000 – 8000 Hot and Cold closed system

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 NON-OXIDIZING BIOCIDE PRODUCT SELECTION

Max Contact
Active Ionic Maintenance
Biocide Type pH Odor Interference Time
Components Charge Dosage ppm
(hrs)
Bulab Morpholine, 50 – 150
SA/MP WSCP/Bronopol 9.5 None Nil 4–6
6068 metaborate
Bulab 35 – 200
MP Isothiazolones 9.5 None Nil H2S 4–6
6057
Bulab Ammonia, 1º&
SA Glutaraldehyde 9.5 None Nil 2–6 100 – 200
6112 2º amines
Bulab slight Metals
MP Carbamates 9.5 Nil 4–6 5 – 20
6013 anionic chromate
Suspended
Bulab solids
SA Cationic polymer 9.5 Nil Cationic 2–4 2 – 20
6002 anionic
polymers
Reducing
Slight agents
Bulab 7.5 –
MP DBNPA bro- Nil pH >8.0 0.5 – 2.0 30 – 100
6042 8.0
mine high
temperature

Bulab
MP TCMTB <8.0 None Nil Sulfides 4-6 2 – 30
6018
Bulab 2 – 10
MP TCMTB/MBT <8.0 None Nil Sulfides 4-6
6010
Bulab 2 – 10
MP Triazine 9.5 Nil Nil - 6–8
6096
Bulab 5 – 30
MP MBT <7.5 Sulfur Nil Ferric ions 6 – 10
6006
Bulab Ammonia, H2S, 5 - 100
MP BHAP 9.5 Slight Nil 2-4
6039 metals
Bulab Slight
SA THPS 10 None Chrome 4–6 75 - 300
6083 cationic
Bulab MBT / TCMTB 450 1 - 2 bags/
MP <8.0 None Nil Sulfides 4-6 4500 gal
6100 grams bag

Bulab MBT / TCMTB 1 –2 bags/

MP <8.0 None Nil Sulfides 4-6 1000 gal
6104 100 grams bag

59
 OXIDIZING BIOCIDE PRODUCT SELECTION

Max Contact
Biocide Active Ionic Maintenance
pH Odor Interference Time
Components Charge Dosage-ppm
(hrs)

Immediate Cont: 0.2 - 0.5

Bulab 6115 BCDMH 9.5 None Nil Organics
FAH

Slug: 0.6 - 1.0

Nil Immediate FAH
Bulab 6041 Sodium bromide 9.5 None Organics
Cont: 0.1 - 0.3
FAH
Slug: 0.6 - 1.0
FAH
Bulab 6073 Sodium chloride 9.5 None Nil Organics Immediate
Cont: 0.1 - 0.3
FAH
Slug: 0.6 - 1.0
Slight
Sodium Nil pH, ammonia, FAH
Bulab 6044C 9.0 chlorin Immediate
hypochlorite amines Cont: 0.2 - 0.5
e
FAH
Slug: 0.6 - 1.0
N/A Slight
Calcium Nil pH ammonia, FAH
9.0 chlorin Immediate
hypochlorite amines Cont: 0.2 - 0.5
e
FAH

Br / Cl Slug: 1 – 5 TAH
Bulab 6054 9.5 None Nil Organics Immediate
Isocyanurate Cont: 1 TAH
Slug: 4 – 10
Bulab 6122 1 drum Bromine 9.5 None Nil Organics Immediate TAH
Cont: 4 – 10 TAH

60
 OTHER (COMPETITOR) BIOCIDES
Active Max Ionic Contact
Type Odor Interferences
Components pH Charge Time (hrs)
Bisthiocyanate M.P. 7.5 Organo-sulphur Nil ferric ions 6 - 10
M.P. / suspended solids
Tin/quat 9.5 Slight amine cat. 2-4
S.A. anionic polymers
Triazine M.P. 9.5 Nil Nil - 6-8
MCI/ M.P. / H2S, ammonia
9.5 Nil Nil 4-6
glutaraldehyde S.A. 1° & 2° amines
Bromonitro -
M.P. 8.5 Slight bromine Nil - 4-6
styrene
Strongly
Phosphonium quat S.A. 9.5 None suspended solids 2-4
cationic
DGH (dodecyl
S.A. 9.0 Nil Cationic anionics 2-4
guanidine HCl)
Dithiol (4,5
dichloro-1,2- M.P. <7.0 Nil 1-2
dithiol-3-one)
metals
Sulfone 9.0 Slight sulfur Nil 4-6
chromate

61