AWT-F-90 (Dec-90)

Association of Water Technologies, Inc.

4th Annual Convention & Exposition
29 November to 1 December 1990
Grosvenor Resort at Walt Disney World Village
Lake Buena Vista, Florida

The Proper Use of Modern Polymer Technology

in Cooling Water Programs

Thomas J. Young
Lubrizol Advanced Materials, Inc.*
Cleveland, OH

Carbosperse™ K-700
Water Treatment Polymers**
© 2008, The Lubrizol Corporation, all rights reserved.
* Formerly BFGoodrich Performance Materials
** Formerly Good-Rite K-700 water treatment polymers
 Abstract

In this paper, modern cooling water treatment technologies have been broken down into
four (4) broad categories. The most common water treatment problems encountered in
each category and some responses to these problems are discussed. These
responses are not necessarily the addition of more chemical but sometimes the removal
of an offending material or a change in the application of the existing treatments. The
strengths and weaknesses of each category are also discussed.

Introduction

There are six (6) dominant technologies is use today for the treatment of open
recirculating cooling water systems. Four of these technologies have been developed
in the last ten years and their application, strengths, and limitations are still somewhat
misunderstood. In all of these technologies, polymers are used and the type, purpose,
level and abilities of these polymers are more or less critical to each of the technologies.

We would like to discuss the four modern technologies, the market niches best
addressed by their capabilities and the most appropriate polymer performance factors to
consider in each application. The six (6) general technologies are as follows:

• "Soft" Phosphate or Dispersant • "Stabilized" Phosphate

• "All Organic" • Molybdate
• Alkaline/Zinc • Chromate/Zinc

Cooling Water Treatment Technologies/Programs

"Soft "Phosphate or Dispersant Programs

In the late 1960s and early 1970s, it became obvious that the chromate-based
technologies in broad use at that time would come under some sort of regulatory
restraint. Early regulation of chromate was based on water pollution by the USEPA but
later OSHA severely restricted worker exposure to the products. More recently,
chromate has been banned by the EPA from comfort cooling towers based on air
pollution criteria resulting from cooling tower drift.1,2

The first chromate replacements were introduced quietly in the early 1970s but
formalized later in the decade.3 The early versions of “soft” phosphate or dispersant
programs incorporated phosphate esters, polyphosphates, and organic phosphates for
scale control. Recent embodiments use only organic phosphates for scale control with
the role of polymers being emphasized in "stressed" conditions. The two variants of this
technology are (1) the dispersant version where the recirculating cooling water Langlier
Saturation Index (LSI) is established at 1.6 to 2.0 and no inorganic phosphate is added
and (2) the "soft" phosphate version where a LSI of 1.6 to 2.0 is not obtainable and

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inorganic phosphates are added to control corrosion. As described in Figure 1, the
solubility of calcium phosphate is not exceeded using "soft" phosphate programs.

Originally, commercial/institutional and light industrial markets the markets were the
focus with this technology. With proper application, the results were and are quite
acceptable in these lower temperature applications, where the heat transfer
metallurgies are generally yellow metal (copper or copper alloy) and the system
availability is not critical to a plant's operation. The weaknesses of the technology were
soon exposed in higher temperatures, high heat flux systems. and in systems serving
mild steel heat exchangers. This technology should not be used under these
conditions; alternate technologies discussed later in the paper should be considered.

When used in an appropriate system, symptoms of misapplication of “soft” phosphate or

dispersant programs are generally limited to (1) calcium phosphate deposition,
(2) calcium phosphonate deposition, and/or (3) corrosion (especially mild steel pitting).
These three failure areas can generally be traced to specific formulation or
misapplication problems that generally are solvable without the use of the more
expensive recent polymer technologies.

Calcium Phosphate Deposition

If calcium phosphate deposition is the recognized foulant in a system, then one of three
things is wrong with the application. The first two variables are usually a function of the
system. They are pH and calcium hardness. If these variables are dictated by the
operation of the system, then the phosphate added with the water treatment should be
optimized just below the solubility allowed by these uncontrolled variables (Figure 1).
By establishing this phosphate level, one eliminates the problem of calcium phosphate
fouling while optimizing corrosion inhibition without unnecessarily increasing the cost of
treating the system.

Should it be possible to control either the pH or cycles of concentration or both in the

system being treated, then these variables can be adjusted to accommodate the
phosphate levels presented by the make-up water or the product. Again, the balance of
these three variables needs to be established at or slightly below the calcium phosphate
solubility described in Figure 1. Doing so will optimize the overall performance of this
technology.

Calcium Phosphonate Deposition

Calcium phosphonate deposition is sometimes encountered in the dispersant version of

this technology where the LSI is established between 1.6 and 2.0 and no inorganic
phosphate is present in the make-up or added with the treatment program. This fouling
is characterized by an analysis that contains approximately equal parts of calcium,
phosphate (as P2O5), and ignition loss. The solution to this problem is to add less

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phosphonate. Generally, three to five parts per million (ppm) of total phosphonate is
adequate to prevent calcium carbonate scaling in the system without resulting in
calcium phosphonate deposition.

In exceptional circumstances, the use of modern polymer technology can alleviate the
deposition of calcium phosphonate in very hot heat exchangers. This is a relatively rare
circumstance that should be avoided to minimize treatment expense and to generally
simplify the treatment approach for these markets.

The dominant need for polymers in this technology is the dispersion of external systems
contaminants such as dirt and dust from the air or iron from the make-up water.
Depending on the treatment approach, we typically recommend polyacrylates (in the
2,000 to 5,000 molecular weight range) that are optimized for dispersion for this
application.

Excessive Corrosion

The third symptom of misapplying this technology is excessive mild steel corrosion.
Assuming the system is not being overchlorinated, then corrosion can be tracked to one
of four causes or application errors (as opposed to a technology weakness) as follows:

1. The use of the dispersant variant of this technology below LSI 1.6. If the
system must be operated below LSI 1.6, then it is appropriate to shift to a "soft"
phosphate program by adding phosphate in an amount indicated by analyzing the
pH / PO4 /Ca-hardness relationship which will eliminate the corrosion problem.

2. Deposition of treatment program by-products on the system surfaces resulting

in under deposit corrosion. The deposition of calcium phosphate or calcium
phosphonate indicates the need to (a) lower the concentration of either phosphate or
phosphonate or (b) adjust the system pH or cycles of concentration to assure
solubility of these materials. Adding more polymer or using higher technology
polymers can mitigate the symptoms but this will not directly address the solubility
problem.

3. The use of the "soft" phosphate version too far below the calcium phosphate
solubility described in Figure 1. The solutions to this problem involve increasing
the pH, the calcium hardness, and/or the inorganic phosphate level up towards the
solubility limit and thereby eliminating the corrosion problem.

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4. The deposition of external materials within the system. This deposition leads to
under-deposit corrosion and must be addressed by either (a) eliminating the source
of the fouling, (b) lowering cycles of concentration to lessen the loading, (c) or using
higher levels of a dispersant polyacrylate.

"Stabilized" Phosphate Programs

In the late 1970s and early 1980s, it was recognized that earlier non-polluting, non-
chromate programs were inadequate for the treatment of high temperature / high heat
flux systems and especially those containing mild steel heat exchangers. "Stabilized"
phosphate programs first introduced and applied in the early 1980s provided a
technological solution to these problems.

The basic concept of stabilized phosphate programs is the establishment of high

inorganic phosphate levels (typically 10 to 20 ppm) and the control of the pH and
calcium hardness at a level where the calcium phosphate solubility is exceeded by
0.3 to 0.6 pH units. The resultant deposition potential is thereby eliminated or controlled
through the use of advanced polymeric materials. When successfully implemented,
“stabilized” phosphate programs can lead to extremely low corrosion and deposition
rates but is absolutely dependent on the levels and types of polymers used.4

Early laboratory work concluded that some polymer variables (e.g., molecular weight),
were not important to the success of these programs.5 While this conclusion appeared
to be correct based on initial laboratory evaluations, early field experience and later
laboratory experimentation showed that both polymer composition and molecular weight
were critical to the success of these stabilized phosphate programs.6,7 More recently,
both polymer and application technology have evolved to accommodate the inevitable
upsets that occur in any cooling water system.8

The two critical dispersion functions required to successfully apply stabilized phosphate
technology are calcium phosphate dispersion or stabilization and, more importantly, the
calcium phosphate dispersion in the presence of iron. Table 1 provides a listing of
deposit control polymers that were evaluated as calcium phosphate inhibitors in the
absence and presence of iron as shown in Figures 2 and 3, respectively. Iron is always
present in industrial cooling water systems and greatly influences both the performance
and selection of deposit control polymers used in stabilized phosphate programs. The
early failings of the stabilized phosphate technology were due to a lack of understanding
the impact of iron in the system. Recent polymer advances minimize the effects of iron
in an otherwise properly controlled system.

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"All-Organic” Programs

As the technical weaknesses of the "soft" phosphate programs spurred the

development of "stabilized" phosphate technology, the economic burden of applying
"stabilized" phosphate programs led to the development of "all organic" programs. In its
simplest form, an "all organic" treatment is nothing more than a strengthened dispersant
program treatment. The concept was to (a) increase the recirculating water LSI of to
2.0 to 2.5 and (b) control the resultant deposition tendencies with better water treatment
chemical programs. The borderline corrosion control achieved in the "dispersant"
program was eliminated by increasing LSI. However, this cause calcium phosphonate
deposition leading to the optimization of dispersant technologies to address higher pH
and calcium phosphonate dispersion.9,10

Calcium phosphonate, specifically calcium-HEDP (1-Hydroxyethylidine 1,1-

diphosphonic acid) and calcium-AMP [Aminotris(methylenephosphonic acid)] salts, are
recognized as problems in this type of treatment program.9,11 There are two ways to
minimize the problems associated with calcium-phosphonate scaling as follows:
1. Using a modern phosphonate such as PBTC (2-Phosphonobutane 1,2,4-
tricarboxylic acid) which is less prone to precipitation, or
2. Using higher performance polymers which disperse or solubilize calcium
phosphonates well enough to prevent fouling (Figure 4).
In actual practice, successful programs generally use both of these approaches.

Early studies that focused on the effects of polyacrylates (PAAs) molecular weight (MW)
on calcium carbonate (CaCO3) showed that (a) low MW PAAs inhibited CaCO3
precipitation from solution and (b) moderate MW PAAs in the presence of precipitated
CaCO3 resulted in cleaner heat exchanger surfaces.12 Modern polymer technology
developments have resulted in not only better dispersants for calcium phosphonates
(Figure 4), but also polymers that are equally effective as antiscalants for controlling
CaCO3 in high temperature heat exchangers.

“All organic” programs that incorporate modern phosphonates and modern polymer
technology can when properly applied generate excellent results more economically and
with greater forgiveness than "stabilized" phosphate programs.

Molybdate-Based Programs

Since about 1986, the use of molybdates in cooling water treatment has been
documented in the literature.13-15 This information has come from two sources; initially,
basic manufacturers promoted the use of molybdates in cooling water programs and
secondarily, the water treatment companies incorporated molybdates into their product
lines. Subsequently, molybdates have been incorporated into other successful
technologies such as the previously discussed "soft" phosphate, "stabilized" phosphate,
dispersant, and "all organic" programs.

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Molybdate-based programs, have spurred considerable discussion as to the value of
molybdate as a corrosion inhibitor and we will not enter into this debate in this paper.
However, there is a consensus that molybdate (a) is an excellent tracer for monitoring
overall product levels and (b) does not contribute to any fouling or other detrimental
performance. To this end, the use of molybdate in a cooling water treatment program
should not affect the polymer choice or the polymer dosage level used. The base
treatment technology should dictate those selections.

Summary

The use of polymers within the various modern cooling water treatment philosophies is
a very complicated issue that should be addressed from an end use application
perspective. Because of its financial and practical considerations, this perspective
leads to treatment designs that minimize the problems generated by poor overall
programs before applying a somewhat more expensive deposit control polymer
technology. We strongly advocate this holistic approach to economical, effective
cooling water treatment design and hope that we can help you in this effort.

References

1. "Regulatory Impacts Analysis for Chromium Emissions from Comfort Cooling

Towers." U.S. Environmental Protection Agency, February 1987.

2. "Chromium Emissions from Industrial Process Cooling Towers," U.S.

Environmental Protection Agency, February, 1986.

3. R.C. May, G.E. Geiger and D.A. Bauer, NACE International, CORROSION, Vol. 20,
No. 4, P. 34 (1981).

4. G.A. Crucil, J.R. Macdonald, and E.B. Smyk, "Role of Polymers in the Mechanisms
and Performance of Phosphate-Based Cooling Water Treatment Programs,"
International Water Conference, Paper No. IWC-87-40, Pittsburgh, PA, 1987.

5. I.E. Woerner and D.R. Boyer, "The Impact of Select Polymers on Calcium
Phosphate Deposition," Corrosion/84, Paper No. 314, NACE International,
Houston, TX (1984).

6. J.E. Hoots and G.A. Crucil, "Role of Polymers in the Mechanisms and Performance
of Alkaline Cooling Water Programs," Corrosion/86, Paper No. 13 NACE
International, Houston, TX (1986).

7. E.B. Smyk, J.E. Hoots, K.P. Fivizzani, and K.E. Fulks, "The Design and Application
of Polymers and Cooling Water Programs," Corrosion/88, Paper No. 14, NACE

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 International, Houston, TX (1988).

8. J.E. Harvey and J.S. Roti, "Handling System Upsets Using High Phosphate
Corrosion Inhibitor Programs: New Polymer Technology Reduces Operating
Problems," Corrosion/88, Paper No. 21, NACE International, Houston, TX (1988).

9. D.A. Little, J.E. Waller and C. Soule,' ”Alkaline All-Organic Cooling Water
Treatment," Cooling Technologies Institute, 1987 Annual Meeting, TP 87-5,
Houston, TX (1987).

10. W.M. Hann and J. Natoli, "Acrylic Acid Polymers and Copolymers as Deposit
Control Agents in Alkaline Cooling Water Systems," Corrosion/84, Paper No. 35,
NACE International, Houston, TX (1984).

11. G.H. Nancollas, "Phosphate Precipitation in Corrosion Protection: Reaction

Mechanisms,” NACE International, CORROSION, 39(3), 77-82, (1983).

12. B.L. Libutti, J.G. Knudsen, R.W. Mueller, "The Effects of Antiscalants on Fouling by
Cooling Water," Corrosion/84, Paper No. 119, NACE International, Houston, TX
(1984).

13. M.S. Vukasovich, "Molybdate: The Versatile Inhibitor," Corrosion/89, Paper

No. 444, NACE International, Houston, TX (1989).

14. K.P. Fivizzani and S.H. Shim, "Effects of Molybdate in Cooling Water Treatment
Programs," Cooling Technologies Institute, 1990 Annual Meeting, TP 90-13,
Houston, TX (1990).

15. C.W. Smith, "Performance of Molybdates as an Alternative to Chromates," Cooling

Technologies Institute, 1989 Annual Meeting, TP 89-10, Houston, TX (1987).

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 Table 1. Deposit Control Polymers Evaluated

Additive Type* Mol. Wt. Comment

K-798 Poly(AA:SA:SS) <15k Carbosperse™ K-700 Polymer**
K-797 Poly(AA:SA:SS) <15k Carbosperse K-700 Polymer
AC3000 Poly(AA:SA:NI) 4.5k*** Competitive terpolymer
AC2000 Poly(AA:SA) 4.5k*** Competitive copolymer
VTL7 Poly(SS:MA) 15k*** Competitive copolymer
BC400 Poly(AA:SA) with phosphinate groups ≈4k*** Competitive copolymer
* Key abbreviations
• AA = acrylic acid, MA = maleic acid, MAA = methacrylic acid, SS = sulfonated styrene
• SA = sulfonic acid (2-acrylamido-2-methylpropane sulfonic acid)
• NI = non-ionic monomer (a substituted acrylamide), N/A = not available
** Supplied by Lubrizol Advanced Materials, Inc.
*** Based on product literature or industry trade association publication data.

Figure 1. Calcium Phosphate Solubility

as a Function of pH and Hardness
9.2
Ca Hardness (ppm )
8.8 2,000 1,000
800 600
8.4
400 300
Maximum pH

8.0 200 100

7.6

7.2

6.8

6.4

6.0
0 5 10 15 20 25 30

Ortho-Phosphate (ppm)
* Based on S. Kubo, T. Takahashi, H. Morinaga, and H. Ueki, "Inhibition of Calcium Phosphate Scale on
Heat Exchanger - The Relationship Betw een Laboratory Test Results and Tests on Heat Transfer
Surfaces, Corrosion/79, NACE International, Paper No. 220, Houston, TX (1979).

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 Figure 2. Calcium Phosphate Inhibition for Various Polymers
100

80
% Inhibition

60

40

20

0
K-798 K-797 AC3000 AC2000 VTL7 BC400

Polymers
9.0 ppm PO4, 140 ppm Ca, pH 8.50, 10 ppm polymer, 50°C, 22 hr

Figure 3. Calcium Phosphate Inhibition in the Presence of Iron

100

80
% Inhibition

No Iron
60
1 ppm Iron

2.5 ppm Iron

40

20

0
K-798 K-797 AC3000 AC2000 VTL7 BC400

Polymers
9.0 ppm PO4, 140 ppm Ca, pH 8.50, 10 ppm polymer, 50°C, 22 hr

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 Figure 4. Calcium Phosphonates Inhibition
for Various Products
100

80
% Inhibition

60

40

20

0
K-798 K-797 AC3000 AC2000 VTL7 BC400
Polymers

15 ppm HEDP, 150 ppm Ca, pH 8.50, 10 ppm polymer, 50°C, 22 hr

Lubrizol Advanced Materials, Inc.

9911 Brecksville Road, Cleveland, OH 44141-3247, U.S.A.
Phone: 1-800-380-5397 or 216-447-5000
FAX: 216-447-6315 (USA Customer Service)
216-447-6144 (International Customer Service)
216-447-5238 (Marketing & Technical Service)
Web Site: www.carbosperse.com
Dec-1990 (Updated Apr-2008)

The information contained herein is believed to be reliable, but no representations, guarantees or warranties of any kind are made to its
accuracy, suitability for particular applications, or the results to be obtained therefrom. The information is based on laboratory work with
small-scale equipment and does not necessarily indicate end product performance. Because of the variations in methods, conditions
and equipment used commercially in processing these materials, no warranties or guarantees are made as to the suitability of the
products for the application disclosed. Full-scale testing and field application performances are the responsibility of the user. Lubrizol
Advanced Materials, Inc. shall not be liable for and the customer assumes all risk and liability of any use or handling or any material
beyond Lubrizol’s direct control. The SELLER MAKES NO WARRANTIES, EXPRESS OR IMPLIED, INCLUDING, BUT NOT LIMITED
TO, THE IMPLIED WARRANTIES OF MERCHANT ABILITY AND FITNESS FOR A PARTICULAR PURPOSE. Nothing contained
herein is to be considered as permission, recommendation, nor as an inducement to practice any patented invention without permission
of the patent owner.
Lubrizol Advanced Materials, Inc.
9911 Brecksville Road, Cleveland, OH 44141, P/216-447-5000, F/216-447-5238
© 2008, The Lubrizol Corporation. All rights reserved.

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