AWT-Sep-2015

Association of Water Technologies

2015 Annual Convention and Exposition
Omni Nashville and Music City Center
Nashville, TN USA
September 9 to 12, 2015

Deposit Control Polymers

for Stressed Phosphate-Based Cooling Water Systems

Libardo Perez, Ph.D.; Zahid Amjad, Ph.D.; and Robert W. Zuhl, P.E.
The Lubrizol Corporation (Wickliffe, OH USA)

Carbosperse™ K-700
Water Treatment Polymers
© 2015, The Lubrizol Corporation. All rights reserved.
 Abstract

Phosphate-based cooling water treatment (CWT) programs are widely used to prevent corrosion on low
carbon steel heat exchangers and piping. Water scarcity and environmental issues have necessitated
cooling system water consumption approaches including operating at higher cycles of concentration (COC)
and using treated municipal or industrial wastewater as makeup water. These water consumption
reduction approaches increase potential fouling and microbiological activity, especially when using
wastewater effluents containing phosphate, other inorganic ionic species (e.g., iron, aluminum, sulfate),
and organic contaminants. This paper presents a technological approach to treat cooling systems
operating under stressed conditions. The paper discusses treatment program efficacy for controlling
metal-phosphate scale formation on equipment surfaces over a wide range of stressed conditions and
compares results to commonly used industrial treatment programs.

Keywords: deposit control polymers, phosphate scale, cooling water, stress conditions, particle dispersion

Introduction

Readily available fresh water sources for industrial uses have decreased dramatically. Accordingly, an
industrial water conservation focus has been operating cooling systems at higher COC, using alternative
makeup water sources (vs. fresh water), and in some cases operating systems at higher temperatures.1

Operating at higher COC increases potential scale and deposit formation in at least two ways.
1. Higher ionic species concentrations might cause scale formation that would otherwise not occur; e.g.,
low levels of calcium and phosphate in the feed water can cause a calcium phosphate scaling problem
when operating at high COC.
2. Increased system holding times (half-life) provide longer time periods for suspended solids to settle on
system surfaces; this may occur during severe droughts and heavy rainfall seasons that may cause
higher suspended solids in makeup waters.

Typically, 10 to 20 mg/L orthophosphate, in combination with polyphosphate and/or zinc ions, is used in
cooling water systems to control low carbon steel (LCS) corrosion. Replacing fresh water makeup with
plant wastewater, reused water, recycled water, or reclaimed water increases potential scaling as well as
corrosion and microbial activity. Phosphate-based scales are typical when using alternative makeup water
sources. Therefore, when using alternative water sources, higher phosphate levels may already be
present, necessitating operating systems at much higher than normal phosphate levels.

Operating cooling systems under these conditions increases the need for robust CWT programs that
prevent calcium phosphate scaling at higher supersaturation conditions as well as disperse suspended
solids at holding times greater than 24 hr. Deposit control polymers (DCPs) have dual roles: (1) inhibit
metal-phosphate precipitation and (2) disperse inorganic suspended solids thereby preventing deposition.
This paper presents performance data for several commercially available DCPs under simulated stressed
cooling water operating conditions caused by high phosphate, high solids, and/or low flow conditions.

Experimental

Solutions were prepared using glassware A, double distilled water, and reagent grade calcium chloride
dihydrate, sodium bicarbonate, magnesium chloride hexa-hydrate, sodium silicate nona-hydrate, sodium
phosphate dodeca-hydrate, and tetra-potassium pyrophosphate. The reagent grade chemicals and
montmorillonite (200 mesh) were obtained from Alfa Aesar. HEDP (1-Hydroxythylidene-1,1-diphosphonic
acid) and TTA (tolyltriazole) were commercial materials obtained from water treatment (WT) industry
suppliers. Calcium and magnesium concentrations were determined by standard EDTA colorimetric
titrations. Silica and phosphate concentrations were determined by spectrophotometric methods (Hach
DR3900).

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Table 1 lists the commercial DCPs evaluated in this study and includes two acrylic acid/sulfonic acid
(AA/SA) copolymers and three AA-based copolymers containing three or more monomers at least one of
which is a sulfonate. All DCP stock solutions were prepared in distilled water on an active solids basis as
were treatment dosages.

Table 1: DCPs Evaluated

Additive Composition MW*
CK775 Poly(acrylic acid: [2-acrylamido-2-methylpropane sulfonic acid]**) or AA/SA with <15k
74/26 monomer weight ratio
CPD20 Poly(AA/SA) with 80/20 monomer weight ratio 4.5k
CK798 Poly(AA : SA : acid: sulfonated styrene) or AA/SA/SS <15k
CPD31 Poly(AA : SA : non-ionic) or AA/SA/NI 4.5k
CPA54 Poly(AA : meth-methacrylate : 2-propene-1-sulfonic acid, 2-methyl- : benzene 15k
sulfonic acid, 4-[(2-methyl-2-propenyl)oxy]-)
* MW = Weight average molecular weight.
** AMPS® monomer supplied by The Lubrizol Corporation.

Three types of tests discussed herein were conducted to assess DCP efficacy as cooling system deposit
control agents.

Static Bottle Testing

Tables 2 and 3 show the static bottle tests (SBT) conditions used to determine DCP efficacy as calcium
and zinc phosphate inhibitors. DCPs were added to solutions containing calcium or zinc and phosphate
ions at the pH studied. The bottles were incubated 24 hr in a 70 °C water bath. The precipitation progress
was determined by spectrophotometric analysis of filtered (0.22 µm membrane) test solution aliquots for
phosphate ion. DCP efficacy was calculated using the following equation:

[PO4] sample – [PO4] control

% Inhibition = x 100 (1)

[PO4] initial – [PO4] control

Where the terms above are as follows:

Inhibition (%) = %I
[PO4] sample = PO4 concentration in the presence of inhibitor at the end of the test
[PO4] control = PO4 concentration in the absence of inhibitor at the end of the test
[PO4] initial = PO4 concentration at the beginning of the test

Table 2: Calcium Phosphate Inhibition SBT Conditions

Parameter Value Parameter Value
[Ca] as CaCO3 400 mg/L Temperature 160 °F (70 °C)
[Mg] as CaCO3 100 mg/L Duration 24 hr
[PO4] as PO4 10 mg/L DCP dosage (as active) 0, 7.5, 10, 12.5,
pH 8.2 and 15 mg/L

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 Table 3: Zinc Phosphate Inhibition SBT Conditions
Parameter Value Parameter Value
[Ca] as CaCO3 300 mg/L Temperature 160 °F (70 °C)
[Zn] as Zn 5.0 mg/L Duration 24 hr
[PO4] as PO4 10 mg/L DCP Dosage (as active) 0, 2.5, 5.0, 7.5,
pH 8.2 and 10 mg/L

Dynamic Dispersion Testing

Dynamic dispersion testing using beakers and gang-stirrer at 10 revolutions per minute (RPM) was used
to determine a DCP’s ability (at 10 mg/L dosages) to disperse suspended solids (i.e., montmorillonite) in
water. Light transmittance readings (%T) were taken at hourly intervals for 7 hr with a Brinkmann® Probe
Colorimeter equipped with a 420 nm filter. The simulated industrial cooling system synthetic water
composition and test conditions for evaluating (“clay” hereafter) dispersion are shown in Table 4. DCP
dispersion efficacy was determined as the transmittance value change vs. the initial value. DCP
performance as percent clay dispersed (%D) was calculated based on %T readings as a function of time
and using Equation 2 which includes an adjustment for readings without DCP present.

%D = [100 - (1.04 x % transmittance)] (2)

Table 4: Dynamic Clay Dispersion Test Conditions

Parameter Value Parameter Value
[Ca] as CaCO3 272 mg/L Temperature 160 °F (70 °C)
[Mg] as CaCO3 120 mg/L Duration 7 hr
[HCO3] as CaCO3 50 mg/L Clay concentration 1,000 mg/L
[Cl] as Cl 1,214 mg/L DCP dosages (as active) 0 and 10 mg/L
pH 7.0 Flow velocity 0.17 fps *
*fps = feet per second

Dynamic Cooling System Testing

A dynamic simulation test rig (DSTR) was used to evaluate DCP efficacy (as scale and fouling control
agents) for cooling systems. The DSTR units were designed to evaluate both scale and corrosion control
under heat transfer and dynamic flow conditions simulating typical cooling system conditions. Bulk water
and heat transfer surface temperatures, pH, and flow velocity were all controlled. Treated synthetic water
was prepared by adding component ions to deionized water. Makeup and blowdown adjustments were
made by continuously feeding synthetic cooling water containing the appropriate treatment to the unit’s
sump. A sump overflow facilitated blowdown. Treatment program efficacy was assessed by the deposit
amount formed at the heat transfer and other surfaces present in the DSTR unit as well as considering
any bulk precipitation (turbidity) and test solution ion concentrations.

Table 5 shows the normal or low stress water chemistry, operating conditions, and the baseline treatment
(BLT1) used for typical condition DSTR experiments. The BLT1 used in all tests included ortho- and pyro-
phosphate to prevent low carbon steel corrosion, tolyltriazole (TTA) to prevent yellow metal corrosion, and
HEDP to prevent potential calcium carbonate deposition. Collectively, the water chemistry, operating
conditions, and BLT1 reflect typical industrial cooling systems.

The DSTR was also operated using the Table 5 water chemistry and operating conditions. However, the
BLT1 was modified by eliminating the 2.4 mg/L pyro-phosphate while increasing the ortho-phosphate
concentration from 14 mg/L to 24 mg/L (BLT2) and 36 mg/L (BLT3) reflecting high and very high stressed
conditions, respectively.

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 Table 5: DSTR Testing Water Chemistry, Operating Conditions, and BLT1
Parameter Value Parameter Value
[Ca] as CaCO3 600 mg/L Clay concentration 0 mg/L
[Mg] as CaCO3 300 mg/L Bulk water temperature 120 °F (48.8 °C)
[HCO3] as CaCO3 50 mg/L Skin temperature 140 °F (60 °C)
pH 7.2 Holding-time index 1.75 days
Ortho-phosphate* as PO4 14 mg/L Hydroxyapatite saturation index**** 14
Pyro-phosphate* as PO4 2.4 mg/L Heat exchanger metallurgy SS** and AB***
Tolyltriazole* (TTA) 4 mg/L Coupon metallurgy AB and LCS
HEDP* 0.6 mg/L Flow velocity 2.75 fps
* BLT1 component. ** SS = Stainless steel. *** Admiralty brass
**** HAP-SI, calculated using French Creek Software’s WaterCycle® Rx program.

Figures 1 and 2 show a DSTR schematic representation and DSTR unit photograph, respectively.

Figure 1: Dynamic System Testing Rig (DSTR) Schematic Diagram

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 Figure 2: DSTR Photograph

Results and Discussion

Static Bottle Testing

Static bottle tests (SBT) were used as a screening tool to quantify DCP efficacy as metal (e.g., Ca, Zn)
phosphate inhibitors. Experience suggest these tests provide a good indication of scale inhibitor efficacy.

Calcium Phosphate Inhibition

Table 2 shows the SBT conditions for evaluating calcium phosphate inhibition as a function of DCP dosage
and Figure 3 presents the data.

Zinc Phosphate Inhibition

Zinc is frequently added to phosphate-based CWT programs to prevent localized (pitting) corrosion on mild
steel surfaces. DCPs are used to control zinc hydroxide and/or zinc phosphate deposition. Table 3 shows
the SBT conditions for evaluating DCP zinc-phosphate inhibition as function of DCP dosage and Figure 4
presents the data.

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 Figure 3: SBT Calcium Phosphate Inhibition vs. DCP Dosage
100

7.5 mg/L 10 mg/L

80 12.5 mg/L 15 mg/L
% Inhibition

60

40

20

0
CK775 CPD20 CK798 CPD31 CPA54

Figure 4: SBT Zinc Phosphate Inhibition vs. DCP Dosage

100
2.5 mg/L 5 mg/L
7.5 mg/L 10 mg/L
80
% Inhibition

60

40

20

0
CK775 CPD20 CK798 CPD31 CPA54

The SBT calcium phosphate and zinc phosphate inhibition data in Figures 3 and 4, respectively lead to the
following collective observations:

1. For the two AA/SA copolymers with different MW and monomer weight ratios, CK775 (74:24)
performed better than CPA20 (80:20) reflecting a combination of higher SA and MW differences.

2. All three AA-based copolymers containing three or more monomers with at least one sulfonate group
performed better than the two AA/SA copolymers. CK798 performing better than both CPA31 and
CPA54.

3. DCP performance increases with dosage and the ranking (highest to lowest) is a follows:
CK798 > CPD31 > CPA54 > CK775 > CPD20

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4. Collectively, these data suggest DCP performance depends upon the several factors including MW,
co-monomers (both type and amount), and manufacturing or polymerization process.2

Dynamic Dispersion Testing

Suspended solids (e.g., clay, silt, and mud) dispersion is essential for preventing deposition on cooling
system surfaces.3 DCP efficacy as a clay dispersant was evaluated under test conditions shown in Table
4. Figure 5 presents four and seven hr clay dispersion data which are representative of the hourly interval
data.

Figure 5: DCP (10mg/L) Clay Dispersion vs. Time

80

4 hr 7 hr

60
% Dispersion

40

20

0
CK775 CPD20 CK798 CPD31 CPA54

Figure 5 dynamic clay dispersion data observations are as follows:

1. For the two AA/SA copolymers with different MW and monomer weight ratios, CK775 (74:24)
performed better than CPA20 (80:20) reflecting a combination of higher SA and MW differences.

2. All three AA-based copolymers containing three or more monomers with at least one sulfonate
performed better than the two AA/SA copolymers. CK798 performed better than both CPA31 and
CPA54.

3. DCP performance decreases with time and the ranking (highest to lowest) was as follows:

CK798 > CPD31 > CPA54 > CK775 > CPD20

4. Collectively, the data suggest that DCP performance depends upon several factors including MW, co-
monomers (both type and amount), and manufacturing or polymerization process.2

Dispersion efficacy loss with time (as shown in Figure 5) is an important consideration when selecting
treatment additives for cooling systems with long holding times, e.g., when operating at high COCs.

Dynamic Cooling System Testing

The DSTRs discussed in the experimental section facilitates evaluating CWT programs under conditions
approximating those found in open recirculating cooling water systems. The DSTR experiments were
designed to simulate both typical and high stress cooling water conditions; the high stress conditions

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include higher ortho-phosphate levels as well as high suspended solids. The SBT and dynamic clay
dispersion evaluations provide a basis for extrapolating potential DSTR DCP rank order of effectiveness.
The DSTR experiments were conducted using different DCP dosages based on experience, with the goal
achieving acceptable performance with at least two DCPs at as low dosage as possible. All DCPs were
evaluated at one or more dosages under each set of DSTR conditions.

The primary DCP role in phosphate-based CWT programs, is maintaining PO4 soluble levels necessary to
facilitate corrosion protection. Therefore, a common operating practice is to maintain the recirculating or
bulk water delta (Δ) PO4 (or difference between non-filtered and filtered PO4) at less than 1 mg/L to prevent
phosphate scaling. Other DSTR performance criteria include low carbon steel (LCS) and admiralty brass
(AB) corrosion rates (CRs) less than one (1) mil per yr (mpy) and clean heat transfer surfaces (HTS) both
stainless steel (SS) and AB. A very slight deposit is referred to as an almost clean surface. Photographs
taken during the experiments illustrate the HTS deposit observations.

Typical Water Conditions

Table 6 shows DSTR results without and with the DCPs listed in Table 1. Duplicate runs with BLT1 and
without DCP present had moderate to heavy deposits on the AB HTS, slight granular deposition on the SS
HTS, 1.5 to 1.9 NTU turbidity, 4.4 mg/L Δ PO4, and negligible metal surface corrosion was observed.

Table 6: DSTR Results - Typical Conditions (e.g., BLT1, HAP-SI @ 14)

Final Final LCS AB
Δ PO4 Turb.* CR** CR SS HTS Deposit AB HTS Deposit
Treatment (mg/L) (NTU) (mpy) (mpy) Observations Observations
BLT1 w/o DCP 4.4 1.5 0.89 0.16 Slight, some granular Moderate to heavy
BLT1 w/o DCP 4.3 1.9 0.78 0.17 Slight, non-uniform Moderate to heavy
2 mg/L CK798 + BLT1 1.3 1.2 0.98 0.17 Very slight spots Very slight
3 mg/L CK798 + BLT1 0.3 0.35 0.76 0.13 Clean Clean
4 mg/L CPD31 + BLT1 0.7 0.78 0.89 0.15 Clean Very slight, non-uniform
5 mg/L CPD31 + BLT1 0.3 0.31 0.74 0.18 Clean Clean
4 mg/L CPA54 + BLT1 0.89 0.84 0.92 0.14 Very slight, non-uniform Very slight, few spots
4 mg/L CK775 + BLT1 0.92 0.97 0.89 0.16 Very slight, non-uniform Very slight, non-uniform
4 mg/L CPD20 + BLT1 1.6 1.1 0.98 0.15 Slight, non-uniform Slight, non-uniform
5 mg/L CPD20 + BLT1 0.45 0.79 0.89 0.16 Clean Very slight, few spots
* Turb. = Turbidity, ** CR = Corrosion Rate

The data clearly indicate that CK798 had the best performance. For example, 3 mg/L CK798 provided
excellent results keeping HTSs clean, 0.3 mg/L Δ PO4, and 0.35 NTU turbidity. Figures 6 (a) and (b) show
clean AB and SS HTSs using 3 mg/L CK798. Table 6 data indicate that the second best performer was
CPD31 requiring a 5 mg/L (67% higher than CK798) dosage to achieve desired results.

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Figure 7 shows results for 4 mg/L CPD31; i.e., the SS HTS was clean but the AB HTS had very slight, non-
uniform deposition. The corresponding data in Table 6 include 0.7 mg/L Δ PO4 and 0.78 NTU turbidity.
CPA54, CK775, and CPD20 at 4 mg/L were not as effective (caused very slight, non-uniform deposit on
both SS and AB HTSs) as either 3 mg/L CK798 or 4 mg/L CPD31 in controlling HTS deposit formation.

Figure 6: DSTR Typical Conditions Using 3 mg/L CK798 at EOE*

(a) AB HTS (b) SS HTS

*EOE = End of experiment

Figure 7:
DSTR Typical Conditions Using 4 mg/L CPD31 – EOE HTSs
AB (Very Slight Deposition) and SS (Clean)

The DSTR typical conditions evaluations indicate that CPD20 provided the least effective performance
among the five DCPs tested as summarized below:

 CPD20 at 4 mg/L was not capable of controlling deposition with slight deposits observed on both SS
and AB HTSs and unacceptable Δ PO4 (1.6 mg/L) and turbidity (1.1 NTU) values were measured.

 Figure 8 compares EOC AB HTSs in the presence of 3 mg/L CK798 and 4 mg/L CPD20.

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 Figure 8: DSTR Typical Conditions – EOE AB HTSs Using Different DCPs
Top - 3 mg/L CK798 (Clean) & Surface and Bottom - 4 mg/L CPD20 (Slight Deposition)

Table 6 results for typical DSTR conditions suggest the DCP performance ranking (highest to lowest) was
as follows:
CK798 > CPD31 > CPA54 ≈ CK775 > CPD20

Stressed Conditions – High Phosphate Make-Up Water

To evaluate DCPs performance under stressed high phosphate conditions, the DSTR was operated using
the Table 5 water chemistry and operating conditions. However, the base line treatment (BLT) was
modified by eliminating the 2.4 mg/L pyro-phosphate and increasing the ortho-phosphate concentration
from 14 mg/L to either 24 mg/L (BLT2) or 36 mg/L (BLT3) reflecting higher stressed conditions.

Table 7 presents results for evaluations conducted using 24 mg/L PO4. The data indicate that 6 mg/L
CK798 provided clean HTSs and 8 mg/L CPD31 (33% higher dosage than CK798) provided similar
performance). The three other DCPs were not capable of providing acceptable results at 9 mg/L dosages.

Table 7: DSTR Results - High PO4 Stress Conditions (BLT2, HAP-SI @ 67)
Final Final LCS
Δ PO4 Turb.* CR** AB CR SS HTS Deposit AB HTS Deposit
Treatment (mg/L) (NTU) (mpy) (mpy) Observations Observations
5 mg/L CK798 + BLT2 1.3 0.98 0.89 0.15 Slight, spots Slight, non-uniform
6 mg/L CK798 + BLT2 0.46 0.52 0.67 0.17 Clean Clean
6 mg/L CPD31 + BLT2 1.5 1.1 0.89 0.14 Slight, non-uniform Slight to moderate
7 mg/L CPD31 + BLT2 1.1 0.78 0.89 0.15 Very slight, non-uniform Very slight, non-uniform
8 mg/L CPD31 + BLT2 0.41 0.58 0.74 0.14 Clean Clean
9 mg/L CPA54 + BLT2 1.2 1.1 0.92 0.15 Very slight, non-uniform Slight, uniform
9 mg/L CK775 + BLT2 1.3 1.2 0.91 0.16 Very slight, uniform Slight, uniform
9 mg/L CPD20 + BLT2 1.4 1.2 1.1 0.16 Some slight spots Moderate
* Turb. = Turbidity, ** CR = Corrosion Rate

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Table 8 presents results for DSTR evaluations conducted using 36 mg/L PO4. The data indicate that DCP
dosages must be increased to achieve acceptable performance under more stress conditions. The lowest
DCP dosages needed to meet the target performance criteria were 10 mg/L CK798 or 12 mg/L CPD31.
The three other DCPs were not capable of providing acceptable results at 12 mg/L dosages.

Table 8: DSTR Results - Very High PO4 Stress Conditions (BLT3, HAP-SI @ 213)
Final Δ Final LCS AB
PO4 Turb.* CR** CR SS HTS Deposit AB HTS Deposit
Treatment (mg/L) (NTU) (mpy) (mpy) Observations Observations
9 mg/L CK798 + BLT3 1.2 0.87 1 0.13 Slight, spots Slight, non-uniform
10 mg/L CK798 + BLT3 0.67 0.54 0.56 0.12 Clean Clean
10 mg/L CPD31 + BLT3 1.5 1.4 0.87 0.15 Slight, non-uniform Moderate
11 mg/L CPD31 + BLT3 0.98 1.2 0.78 0.17 Very slight, non-uniform Very slight, uniform
12 mg/L CPD31 + BLT3 0.56 0.65 0.54 0.14 Clean Clean
12 mg/L CPA54 + BLT3 1.1 0.89 0.87 0.18 Slight, non-uniform Slight, uniform
12 mg/L CK775 + BLT3 1.2 1.1 0.79 0.14 Slight, uniform Slight, uniform
12 mg/L CPD20 + BLT3 1.6 1.3 0.93 0.13 Slight, spots Moderate
* Turb. = Turbidity, ** CR = Corrosion Rate

Very High Stress Conditions – High Phosphate and Suspended Clay Make-Up Water
Clay and silt are common cooling water makeup contaminants during droughts and heavy rainfall periods.
Both clay (containing aluminum silicate) and high phosphate levels when encountered in cooling water
makeup create additional stress and necessitate higher DCP dosages to maintain acceptable results.

To simulate these high stress conditions and evaluate DCP performance, the DSTR units were operated
(a) using the Table 5 water chemistry and operating conditions, (b) the BLT was modified by eliminating
the 2.4 mg/L pyro-phosphate and increasing the orthophosphate concentration to 36 mg/L (BLT3), and (c)
with 50 mg/L clay present. Table 9 presents DSTR results for these very high stress conditions.

Table 9: DSTR Results - Very High Stress Conditions and Clay

(BLT3 and 50 mg/L Clay, HAP-SI @ 213)
Final Initial Final LCS AB
Δ PO4 Turb.* Turb. CR** CR SS HTS Deposit AB HTS Deposit
Treatment (mg/L) (NTU) (NTU) (mpy) (mpy) Observations Observations
10 mg/L CK798 + BLT3 1.20 10.4 4.63 0.78 0.19 Slight, non-uniform Slight, non-uniform
11 mg/L CK798 + BLT3 0.67 10.2 6.54 0.87 0.20 Clean Very slight, uniform
13 mg/L CPD31 + BLT3 1.50 9.8 3.62 0.92 0.15 Slight, non-uniform Moderate
15 mg/L CPD31 + BLT3 0.98 10.1 4.8 0.92 0.21 Very slight, non-uniform Very slight, uniform
15 mg/L CPA54 + BLT3 1.60 10.3 3.97 0.97 0.19 Slight, spots Moderate
15 mg/L CK775 + BLT3 1.10 10.1 3.52 1.03 0.18 Slight, non-uniform Moderate
15 mg/L CPD20 + BLT3 1.86 10.5 2.86 1.20 0.24 Moderate Heavy
* Turb. = Turbidity, ** CR= Corrosion Rate

Under these very high stress conditions, 11 mg/L CK798 (10% higher than without clay present) provided
acceptable deposit control. Figure 9 shows the corresponding insignificant HTS deposits and acceptable
corrosion coupons (CCs) for both AB and SS.

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 Figure 9: DSTR Very High Stress Conditions and Clay (BLT3 and 50 mg/L Clay)
EOE Using 11 mg/L CK798 - AB (left) and SS (right) HTSs and CCs

By comparison, CPD31 at 13 mg/L provided unacceptable deposit control but when increased to 15 mg/L
(36% higher than CK798) provided acceptable results and less than 1 mg/L Δ PO4. CPA54, CK775, and
CPD20) at 15 mg/L dosages failed to provide acceptable deposit control. CPD20 was clearly the worst
performer with moderate to heavy HTS deposits; see Figure 10 showing HTSs as function of time.

Figure 10: DSTR Very High Stress Conditions (36 mg/L PO4 and 50 mg/L Clay)
Using 15 mg/L CPD20 – HTSs vs. Time
(a) Day Two (b) Day Three

(c) Day Four (d) EOE

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For the very high stress DSTR conditions with clay (i.e., 36 mg/L PO4 and 50 mg/L clay), the DCP
performance ranking (highest to lowest) was as follows:

CK798 > CPD31 > CPA54 ≈ CK775 > CPD20

Summary

Our observations and conclusions based on industry trends and laboratory work discussed here are as
follows:

1. The need for high performance DCPs as component of phosphate-based CWT programs is growing
due to decreasing water quality available for industrial cooling system make up and increases in water
recycle and reuse.

2. Static bottle tests (SBTs), dynamic clay dispersion tests (DCDTs), and several dynamic simulation test
rig (DSTR) conditions (typical, high stress [HS], very HS, and very HS with clay) were used to evaluate
commercially available DCPs as CWT program components. Five (5) DCPs were evaluated including
two AA/AMPS copolymers and three AA-based copolymers containing three or more monomers (at
least one which is a sulfonate). There is good agreement between the SBT, DCDT, and DSTR
evaluation results. Collectively, the laboratory testing suggests that DCP performance increases with
dosage and the ranking (highest to lowest) was as follows:

Overall: CK798 > CDP31 > CPA54 > CK775 > CPD20
Groups: AA-based copolymers plus > AA/SA copolymers

3. Data presented herein suggest that DCP performance strongly depends upon several factors including
molecular weight and co-monomers (both type and relative amounts).

4. CK798 is well suited for use as a high performance component of stressed phosphate-based CWT
programs.

Acknowledgements

The authors thank John Zibrida for the WaterCycle Rx program calculations and The Lubrizol Corporation
for permission and support to conduct this study and present the results to the Association of Water
Technologies.

References

1. L. A. Perez and D. T. Freese, “Scale Prevention at High LSI, High Cycles, and High pH without the
Need for Acid Feed,” CORROSION 1997, Paper No 174 (Houston, TX: NACE 1997).

2. R. W. Zuhl and Z. Amjad, “The Role of Polymers in water Treatment Applications and Criteria for
Comparing Alternatives,” 5th Annual Convention and Exposition, Las Vegas, NV, 1993.

3. L. A. Perez and S. M. Kessler, “Novel calcium Phosphate Scale Inhibitor,” in Water soluble Polymers
Solution Properties and Applications, ed. by Z. Amjad, Plenum Press, N.Y., pp 149-161, 1998.

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Sep-2015
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