# %

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Chapter – 
ORGANIC POLYMERS AND THEIR ROLE
AS SCALE INHIBITORS, DISPERSANTS
AND SLUDGE CONDITIONERS IN
BOILER WATER TREATMENT
The role of polymers in internal boiler water treatment is significant. That too, the recent introduction
of synthetic polymers have totally changed the face of boiler water treatment. Not only they replace the older
chemicals including natural ones but offer too many advantages. They are remarkable scale and corrosion
control agents. They perform various functions such as solubilization, dispersion, agglomeration, and crystal
distortion and sludge conditioning. Because they perform such important functions, they provide the cleanest
tube surfaces than any other available internal treatment programs and hence heat transfer rates are
maximized. Since synthetic organic polymers solubilize calcium, magnesium and aluminium and maintain silica
in solution, corrosion potential side effects are also avoided. Still another advantage is that iron particulates
(returned from condensate) are dispersed by these polymers and are easily removed by blowdown.

The role of polymers have been discussed then and there in the appropriate contexts but an exclusive
chapter is devoted to shower many more information and their multifarious application in boiler water
treatment. Before dealing with the specific applications, an introduction on the polymers is given which
provides a basic idea about polymers and the mechanism of reactions when these polymers are applied.

Polymers are organic macromolecules (long chained sometimes branched) containing a number of
repeating small identical subunits (ionizable functional groups). Sometimes they contain two or three different
+ +
kinds of subunits. The subunits contain ionizable groups such as – COOH, -OH, -NH2 , R1NR2 and POP3H2.
6
Long chain molecules of this kind may be produced to contain from 2 to 3 to nearly 10 subunits.

Synthetic polymers are formed by polymerization of small substances, known as monomers. When
the monomers are the same substance the resulting polymer is termed as homopolymer. If two or more three
different groups (or units) are polymerized together, the resultant product is known as copolymer.

For example, let us consider the polymerization of acryl amide resulting in a homopolymer.

Acrylamide monomer is CH2 = CH – CONH2

The building unit can be written as

CH2 = CH
|
O = C – NH2
# && Organic Polymers
On polymerization, several molecules unite together to yield the homopolymer, polyacrylamide.
– CH2 – CH – CH2 – CH – CH2 – CH –
| | |
O = C – NH2 O = C – NH2 O = C – NH2

Two different monomers can be polymerized to yield a copolymer. For example, acryl amide is
polymerized with acrylic acid to form a copolymer polyacrylamide co-acrylic acid.

Acrylamide monomer : CH2 – CH

|
O = C – NH2

Acrylic acid monomer : CH2 – CH

|
O = C – OH

Resulting copolymer is polyacrylamide co-acrylic acid

– CH2 – CH – CH2 – CH –
| |
O = C – NH2 O = C – OH

A great variety of monomers can be polymerized in this manner. To suit the specific requirements, the
polymers can be tailored to obtain a product with different functional groups, molecular weights and electrical
charge. This can be achieved by selecting suitable monomers carefully and combining them in the right
proportion. In addition to the functional groups present ,molecular weight and electrical charge are the deciding
factors in the selection of a polymer for a particular application in water and waste water treatment. Molecular
weight of polymers range from 1000 to several million and it greatly changes the properties of a polymer (and
subsequently its application in water treatment).

Based on the electrical charge they carry, polymers are divided into three groups.

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Cationic polymers have an excess positive sites (attracting anions) over negative sites or only positive
sites. Anionic polymers have an excess of negative sites over positive sites or only negative sites. Non-ionic
polymers have an equal distribution of positive and negative sites or no ionized sites. A few examples for each
category are given below:
 Organic Polymers # '
'
Cationic Polymer
– CH2 – CH – CH2 – CH – CH2 –

+ +
N N
R R
Polyvinyl pyridinium salt

Anionic Polymer
– CH2 – CH – CH2 – CH – CH2 – CH –
| | |
– – –
COO COO COO
Polyacrylate

CH3 CH3 CH3

| | |
– CH2 – C – CH2 – C – CH2 – C –
| | |
– – –
COO COO COO
Polymethacrylate

Non-ionic Polymer
– NH – CH – CO – NH – CH – CO – NH – CH – CO –
| | |
(CH2)4 (CH2)2 (CH2)4
| | |
+ – +
NH3 COO NH3
Polylysine glutamic acid

As indicated already, these polymers∗ have totally changed the face of water treatment in general and
boiler water treatment in particular.

Cationic polymers with high charge density are used as primary coagulants. A smaller dose, say 0.3
to 3 ppm is sufficient to clarify water. Hence this organic treatment is economical than inorganic coagulation
using alum and ferric salts. Another major application of cationic polymer is in the flocculation of waste water
particles. High molecular weight copolymers are used for this purpose.

Anionic polymers play a vital role in water treatment. As regards external treatment, they are
employed as effective flocculation aids. High molecular weight anionic homopolymers and copolymers are

∗
Polymers have enormous applications in industries – as flocculants, additives, flooding agents and friction reducers in mineral
processing, paper making, oil recovery etc., - to name a few.
# (
( Organic Polymers
used for this purpose. In lime-soda softening also it is sometimes added as flocculation aid. In boiler water
treatment, they are used for scale inhibition, dispersion, sludge conditioning and also to reduce iron deposition.

Non-ionic polymers are also effective flocculation–aids. When aluminium or ferric salts are used as
primary coagulants, the turbidity in the effluent from the clarifier can often be reduced by supplementing the
inorganic coagulants with 0.1 – 0.5 ppm of a non-ionic polymer. In the silica removal by precipitation method
(lime-soda softening), non-ionic polymer emulsion is added to control carryover of silica. It is reported to be
more advantageous than the conventional sodium aluminate. Polymers proved to be more efficient and
convenient to use.

A wide variety of synthetic polymers are now used for internal boiler water treatment. They primarily
act as scale inhibitors, disperants, and sludge conditioners. Some of the polymers accomplish all these three
jobs, while some others do one or two functions only. The role of these polymers in carryingout these functions
and the mechanism behind such reactions are discussed elaborately in the following sections.

POLYMERS AS SCALE INHIBITORS

The scales that would be normally formed in boiler are calcium carbonate, calcium sulfate and
calcium phosphate. The use of polymers at recent times as scale inhibiting agents in boiler water treatment
has solved many problems associated with these scales. Infact, polymers do not form any soluble complexes.
Instead, the water scaling ingredients are allowed to precipitate. The polymers distort or modify the scale
crystals such that they cannot adhere to each other to form a hard deposit. Instead, they become a sludge that
can be easily removed by blow down. Besides, the introduction of polymer in the crystallire lattice does not
allow the crystals to adhere to the surfaces too where it could cause heat transfer problems.

These polymers inhibit all types of calcium scales. They are stable even in the presence of high
concentrations of acids and alkalies and do not breakdown. They do not contain halogens, phosphorus or
heavy metals and are environmentally acceptable.

The scale control abilities of a polymer are determined by its functional groups, the organic molecular
structure, the charge density it carries and orientation of the functional groups. The most commonly used
polymers for scale inhibition are anionic low molecular weight compounds. The two prominent anionic
polymers are polyacrylate∗ and polymethacrylate∗.

CH3
|
– CH2 – CH – – CH2 – C –
| |
C=O C=O
| |
– –
O n O n
Polyacrylate Polymethacrylate

∗
These two polymers act not only as scale inhibitors but also as dispersants and sludge conditioners.
 Organic Polymers # )
)
Polyacrylate with molecular weight in the range of 5000 – 10000 is sometimes described as an
antiprecipitant because a complex (not a chelonate) forms between calcium ions and the carboxyl groups.
Satisfactory dosages of polyacrylates in general, are 10–15 ppm below 500 psi and 5– 10 ppm from 500 to 900
psi.

It is to be mentioned that the recent scale inhibiting formulations include more than one type of
polymer. They are blends of select chemicals intended to control specific mineral scales, namely, calcium –
carbonate, calcium sulfate and calcium phosphate. For control of calcium carbonate, homopolymers such as
polyacrylates, polymethacrylates and polymaleate are used. Use of a copolymer of acrylate and acrylamide is
reported to be more effective in controlling calcium sulfate scale. Certain polymeric formulations also include
phosphonates to achieve much more effective results. Addition of phosphonates (HEDP∗ / PBTC∗∗) also helps
to control calcium phosphate scale. These new formulations provide best possible scale prevention of any kind
in comparison to conventional chemicals.

POLYMERS AS DISPERSANTS

Formation of sludge in boiler water is as serious as scale formation. If sludge formation is not
prevented, it may settle to form deposits, accumulate in areas where the flow of water is slow and interferes
with circulation. At high pressures, sludge may bake on boiler tubes or form porous deposits that can cause
corrosion within the boiler. Addition of natural or synthetic polymers to boiler water, condition these particulates
so that they do not form large crystalline precipitates. Polymers used for this purpose are termed as
‘dispersants’. As the name implies dispersants promote the suspension of insoluble salts (especially calcium
and magnesium phosphates) in the bulk of circulating water and never allow to agglomerate into a mass and
consequently they cannot stick to heat transfer surfaces. The mechanism behind such dispersion can be
illustrated as follows: After an insoluble particle has formed, the polymer enters into a surface reaction with it
(i.e.) the dispersants coat the particles to form a clarified colloidal solution that can be controlled by continuous
blow down. They are reported to fluidize sludge for easy removal. Thus the accumulation of sludge is
prevented so that the heat transfer surfaces are kept clean.

Various dispersants are added to disperse insoluble materials. They are classified as natural and
synthetic dispersants.

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This group includes,

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∗
HEDP – (1 – hydroxyl ethylidene 1, 1 – diphosphonic acid)
∗∗
PBTC – (2 – phosphono butane – 1, 2, 4 – tricarboxylic acid)
#!  Organic Polymers
As indicated above, these dispersants form colloidal aqueous solutions and fluidize insoluble matter in
water.

Tannin forms a dense, non-adherant floc with calcium carbonate and magnesium hydroxide that can
be removed from the boiler by intermittent blow down. When colloidal particles are present, tannin encloses
them in a protective envelope that prevents their coagulation by electrolytes. Condensed tannins are useful for
low pressure boilers containing 200 – 400 ppm suspended solids.

Sulfonated lignins are economical dispersants for phosphates and iron oxides. They too are protective
colloids. They act by coating particles to form a clarified colloidal solution. It is to be noted that sulfonated
lignins tend to form carbonized deposits in sections at high temperature. These products begin to char at about
O
260 C.

It is reported that combination of these polymers are more effective rather than used singly.
Recommended dosages are tabulated below:

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It is to be noted that these conditioners can be added along with phosphates. Despite their
advantages, lignins and tannins are not suitable for boilers operating above 600 psi, as they char at the
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temperature of 260 C as indicated above.

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The above mentioned natural dispersants no doubt are excellent in their performance. But they are
slowly replaced at present with synthetic polymers owing to their high efficiency and thermal stability. The most
commonly employed synthetic polymers are, polyacrylate, copolymers of polymethacrylate, polymaleate,
sulfonated styrene and polyacrylamide. For effective dispersion, low molecular weight polymers are employed.
Both anionic and non–ionic polymers are effective dispersants.

Among the important dispersants, namely polyacrylate and polymethacrylate, polyacrylate is reported to
be the best performer. In the pressure range from 90 to 600 psi, sodium polyacrylate outperforms sodium –
polymethacrylate (except at low molecular weights). It should be noted however, that application of these
polymers is also limited to pressures below 1000 psi. At pressures upto 1800 psi heat stable polymers such as
anionic carboxylates and their derivatives are used for effective dispersion. An alkaline environment generally
increases their effectiveness.

Note: While dispersants are capable of dispersing all the insolubles, basic phosphates of magnesium do not respond well
to the dispersants and tend to stick to hot metal surface.
 Organic Polymers #!!
#!!
Dispersants are also added when sodium carbonate is employed to precipitate hardness. Addition of
dispersants prevents the formation of calcium carbonate layer on evaporative surfaces.

POLYMERS AS SLUDGE INHIBITORS / SLUDGE CONDITIONERS

Despite the best treatment applied to boiler water, some suspended solids may present in it. This
apart, corrosion products from condensate returns enter into boiler system as suspended solids. They present
in boiler water as loose, soft deposits in the mud drum and water wall headers. If this sludge is not dispersed
using sludge conditioners, they may settle to form deposits and these deposits may bake impeding the
circulation of water at these critical sections. Suitable polymeric substances are added to boiler water to
condition these particulates so that they do not form large crystalline precipitates and remain as smaller
particles. A wide variety of natural organic materials and synthetic polymers are used for this purpose.

Natural materials include, tannin lignin and starches. Tannin plays a dual role in the control of sludge.
It minimizes the sludge and also absorbs a small amount of dissolved oxygen and thus contributes to corrosion
control too. It helps to form a protective film on mild steel surfaces. However, the dosage requirement is very
high. To be more effective, several hundred ppm of tannin is required. Hence it is applicable to low pressure
boilers only. For boilers of intermediate pressures, lignin compounds such as sulfonated lignin are used.

These natural sludge conditioners are replaced at recent times with synthetic polymers. Some of the
widely employed water–soluble synthetic polymers are, polyacrylate, copolymers of methacrylate and
sulfonated styrene. These synthetic polymers have been shown to be more cost effective than tannins and
lignins. The dosage requirement of these synthetic material is much less (i.e.) 5 – 20 ppm only.

Polyacrylates and polymethacrylates are effective in both the carbonate and phosphate treatment
programs. Their high thermal stability make them suitable for boilers at pressures of 800 psi or higher (upto
1000 psi). However, they too are decomposed at higher temperatures. Neither of these polymers show any
o o
sign of decomposition upto 345 C. Above this temperature charring begins and is completed at 540 C. Hence
for boilers of pressures upto 1800 psi, heat stable polymers such as anionic carboxylates and their derivatives
are used as effective conditioning agents. An alkaline environment generally increases their effectiveness.

The only drawback encountered with synthetic polymers is their limited effectiveness in controlling
iron-oxide deposition.

Some of the suggested mechanisms by which polymers act as sludge inhibitors / conditioners are
given below:

1) Increasing the solubility of some slightly soluble compounds. Polyacrylates do this job well.

2) Another mechanism is interfering in the process of crystallization. Polyacrylate, polymethacrylate,

polymeleate restrain effectively the particles from crystallization.

3) Yet another mechanism is limiting the size of crystal. It is reported that sulfonated polymers effectively limit
the size of calcium and magnesium salts while the carboxylated polymers limit the size of ferric hydroxide
particles.
#!"
#!" Organic Polymers

4) Dispersion of insoluble particles is also considered as an effective mechanism.

In addition to the functions described above, polymers offer several advantages in boiler water
treatment. For example, polyacrylates prevent the accumulation of ‘oil balls’ and the formation of sticky oil
sludges. Addition of polymers as scale control agents increases the effectiveness of chelant programs. As
regards external water treatment, they are extensively used as coagulants and flocculation-aids. The role of
polymers in such functions has been dealt exhaustively in Chapter - 29.

PHOSPHONATES

Phosphonates are a class of organic compounds used in water treatment. They are also termed as
‘organic phosphates’. At recent times they are extensively used in various industrial water treatment
processes. They function as antiscalants, corrosion inhibitors, chelants, sludge conditioners, dispersants and
deflocculants. In boiler water treatment they are essentially used as scale and corrosion inhibitors. They are
available in various formulations as acids or salts. The most frequently used phosphonates are:

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The chemical reactions of all these phosphonates are similar; however their stability varies greatly.
For more details on the applications of phosphonates refer the section, “Phosphonate Program” under
Chapter-46.