Reprint R-816

Methods to Monitor and Control Scale in

Cooling Water Systems
By B. E. Moriarty, J. P. Rasimas, P. R. Young and J. E. Hoots, Ondeo Nalco Company

ABSTRACT Table 1 —Selected list of treatment actives that can be

monitored/controlled by on-line fluorescence methods
This paper describes two novel methods to monitor
the activity of scale control programs used for treat- Treatment Actives Performance Function
ment of open recirculating cooling water systems. The
Ortho-phosphate Corrosion inhibitor
first technique is a reagent based at-line colorimetric
method that provides a fundamental understanding Inorganic phosphates Scale/corrosion inhibitor
of the treatment program performance. Also detailed (e.g., pyrophosphate)
is a reagentless, on-line fluorometric method that directly Zinc Corrosion inhibitor
determines program performance and allows ad- Azoles Copper (alloy) corrosion inhibitor
vanced control strategies of both the treatment program
Organic phosphonates Scale inhibitor
and system operation. Evidence is shown that the loss
or consumption of the polymer is a sensitive measure Tagged polymeric Stabilizes other treatment
of the scaling tendency of a cooling water system. dispersant actives and particulates/silt
Finally, the use and benefits of polymer consumption dispersant
to control a cooling system to save water and mini-
mize scale under upset conditions is demonstrated.

INTRODUCTION
Treatment programs have been applied to cooling
water systems for many years. The treatment program
contains active components (“actives”) that serve to
minimize performance problems, such as scaling, cor-
rosion, fouling, and microbiological growth. Table 1
lists a variety of treatment actives and their func-
tions.1–6 The control of treatment programs is impor-
tant to ensure that the desired amount of actives is
present. A previous paper discussed using an inert
tracer within the treatment program to control the
product dosage to the cooling water system.7 Using
Figure 1 — Generalized representation depicting the
an inert tracer, the amount of product added to the correlation between performance problems and
cooling system is accurately known; however, this does treatment actives consumption (as scale/deposits
not insure that, under stressed conditions, system form due to high stress conditions).
problems will not occur. If the correct amount of prod-
uct has been fed and active residual levels are low, it is and adsorbing onto solids/surfaces in the system,
likely that the system has responded to a stress.1–6,10–13 thereby acting to prevent growth of scale/deposits and
This also provides an opportunity to take corrective enhancing performance of corrosion inhibitors (Fig-
action to reduce the system stress or modify the treat- ure 1).10 In the process of preventing scale/deposits/
ment program. corrosion, a limited amount of scale inhibitor con-
Scale inhibitors are pivotal to the performance of sumption will naturally occur [Table 2 (“Normal” col-
many treatment programs.8–9 Scale inhibitors function umn) and Figure 1(left half)].1–6 As scale/deposits form
by adsorbing onto suspended solids/scaling particles

Presented at Corrosion/2001, Houston, Texas, March 11–16, 2001

Table 2 — Sources of system consumption of treatment
actives
Normal Undesirable
Forming Protective Films Scale Formation
Repair of Protective Films Deposition
Scale, Deposit Inhibition Corrosion Products
Dispersing Corrosion Products Fouling
Limiting Microbiological Growth Microbiological Growth
Particulate Dispersion Degradation of Actives
Inhibiting Deposition of Soluble
Corrosion Products
(e.g., as a result of high-stress operating conditions),
inhibitors will be incorporated into the particles, and
concurrently be observed as consumption of the treat-
ment actives. As there is a “normal” level of consump-
tion of treatment actives, an increase above this level
of consumption can be indicative of a system stress
and early warning of imminent performance problems
[Table 2 (“Undesirable” column) and Figure 1 (right
half)].1–6
There are other modes of consumption beyond sys-
tem stresses. For example, the phosphonate-based
scale/corrosion inhibitor, 1-hydroxyethylidene-1,
1-diphosphonic acid (HEDP), can be degraded by
excessive levels of oxidizing biocides. As the concen-
tration of HEDP is decreased (which increases treat-
ment costs to replace the lost actives), scaling/corro-
sion can occur if there is an insufficient level of HEDP.
A common component of many cooling water treat-
ment programs is a dispersant polymer. (See Table 1.)
These polymers prevent deposits because they keep
suspended particles from adhering to pipes, tubes, or
other surfaces in the cooling system and are removed
with the water by blowdown. In order to be effective,
the polymers must strongly adhere to the particle sur-
faces so that the polymer’s fate is the same as the
particle it is bound to. In a scaling event, polymers
become part of the deposit, or are removed from a
cooling system via system blowdown. The exact
mechanism (co-precipitation, adsorption, etc.) of this
inclusion is not fully understood, but the phenomenon
is quite general.
The amount of polymer necessary is a complex func-
tion of hardness, temperature, pH, and many other
factors.14 Much of this is due to the increased ther-
modynamic “driving force” for precipitation of calcium
carbonate or calcium phosphate. At high bulk water
temperatures (>60°C), high calcium concentrations
(>750 mg/L as CaCO3), or low flow rates (<1 m/sec),
the tendency for scale formation, even with cooling
water treatment programs, is greatly increased. As
the system water chemistry becomes more stressed,
2
so does the necessity for increased levels of active
polymer. Recently, an improved dispersant polymer
has been developed that is much more tolerant of such
stresses.15 This can improve the performance of a pro-
gram under high stress conditions with lower doses
of polymer, but opportunities for further optimization
still exist.
There are also other variables that can change the
system demand for polymer. There are different heat
loads during day/night operation, seasonal variations,
and ambient weather changes. It is impossible to pre-
cisely predict the polymer demand a priori; therefore,
upset conditions may occur without notice. If poly-
mer is underdosed, serious scale formation may re-
sult. A practical solution to this problem is to dose
sufficient polymer to respond to a worst-case scenario;
however, this practice can often result in overdosing
of polymer. Inert tracer technology maintains prod-
uct feed at the recommended dose and hydraulic
changes (both known and uncontrolled) can be easily
accounted for. However, in a system with severe and
variable stresses, there will be additional opportuni-
ties to enhance/optimize performance, provided a
measure of treatment actives is possible.
System stresses and consumption of treatment actives
precede significant performance losses, as shown sche-
matically in Figure 2. By responding to consumption
of treatment actives before system performance prob-
lems occur (pre-acting), loss of system performance
can be prevented. That corrective response can be a
change in treatment dosage, a change in operating
conditions (e.g., cycles of concentration, pH, etc.), or
other response.13
The focus of this paper will be improving the scale
inhibition performance of a cooling water program
by monitoring consumption of the dispersant poly-
mer relative to the inhibitor program dosage. First,
we will show some data that indicates that treatment
Figure 2 — Generalized representation depicting on-
line measurement of actives consumption (resulting
from high system stress). In this case, consumption
precedes performance problems.
Table 3 — Operating conditions for pilot cooling Table 4 — Composition of make-up waters used in pilot
tower tests cooling tower testing

Parameter Conditions Make-Up Water

Metallurgy of Heat Mild Steel, Admiralty and Used for Hours

Exchangers Stainless Steel PCT PCT 150-350 of
Test 1-4 Tests 5-10 PCT Test 7
Basin Water All-Organic (Tests 1-7) – 32
Temperature (°C) Stabilized Phosphate (Tests 8-10) – 43 Ca+2 (mg/L as CaCO3) 90 150 300
Return All-Organic (Tests 1-7) – 38 Mg+2 (mg/L as CaCO3) 50 75 150
Temperature (°C) Stabilized Phosphate (Tests 8-10) – 49 Total Alkalinity
pH All-Organic (Tests 1-7) Uncontrolled (mg/L as CaCO3) 110 110 110
at ~ 9 Sulfate (mg/L as SO4) 50 70 250
Stabilized Phosphate (Tests 8-10) –
Conductivity (µS/cm) 500 670 1190
Controlled at 7.0
Heat Load (W/m2) 15,760 – 39,085
Concentration Ratio Generally 4
Table 5 — All-organic program in pilot cooling tower
Flow rate (L/m) All-Organic (Tests 1-7) – 7.6 tests 1 – 3* – analysis of heat-exchanger deposits
Stabilized Phosphate (Tests 8-10) – 6.4
% Composition of Deposit
+2
Test # Ca CO3+2 HEDP PBTC Polymer Deposit Rate
actives were consumed and appeared in the deposits 1 21% 16% 10% 9% 10% 80 mg/day
from heat exchanger tubes. Then, a new colorimetric
2 20% 15% 11% 10% 10% 112 mg/day
method will be presented for the measurement of
3 20% 19% 9% 12% 10% 15 mg/day
active polymer in a cooling water system. Next, the
use of fluorescent dispersant polymers will be dis- Avg 20% 17% 10% 10% 10%
cussed. Finally, we will demonstrate that on-line
determination of polymer consumption can be used Table 6 — All-organic program in pilot cooling tower
to optimize control and improve performance in cool- test 4 – ratio of substances in bulk cooling water and
ing water systems. heat-exchanger deposits
% Ratio of Dosage of
EXPERIMENTAL PROCEDURES Substances in Substances
Average PCT (as ppm) in
A general description of the Pilot Cooling Tower (PCT) Deposit*,** Bulk Water
has been previously reported.16 The general operat-
Ca+2 2 240
ing and heat exchanger tube conditions are given in
+2
Table 3. The make-up water conditions are given in CO 3
1.7 140
Table 4. HEDP 1 4.2
PBTC 1 6
EXAMPLES OF CONSUMPTION Polymeric Dispersant 1 7.5
IN COOLING WATER SYSTEMS
**Deposit is enriched in HEDP, PBTC and Polymeric Dispersant vs.
As shown schematically in Figure 1, treatment actives **Calcium, Alkalinity; as compared to bulk water composition.
(e.g., polymeric dispersants and scale-inhibiting **If 1 ppm of HEDP (24% loss from bulk water) is consumed due
phosphonates) adsorb onto scale-forming particulates to deposit formation, then only 2 ppm of calcium (0.8% loss from
and surfaces to help prevent scale/deposit formation. bulk water) and 1.7 ppm of carbonate (1.2% loss from bulk water)
would also be consumed in the formation of that deposit.
If scale/deposits start to form as a result of high-stress
operating conditions, the treatment actives will in-
corporate into those particulates. Therefore, by ana- As indicated in Table 6 (data from PCT test 4), con-
lyzing the deposits from cooling water systems, we sumption of treatment actives [e.g., HEDP, 2-phos-
can verify that treatment actives are present. Analy- phonobutane-1, 2,4-tricarboxylic acid (PBTC), and
ses of the deposits from Pilot Cooling Tower tests (PCT polymeric dispersant] is much more sensitive to the
Tests 1–3) of an All-Organic treatment program re- early formation of deposits than other chemical com-
vealed that a consistent level of treatment actives was ponents of the bulk water, such as calcium and alka-
present over a range of deposit rates (Table 5).16 linity. This is because the deposit is enriched in the
Deposit analysis shows enrichment of polymeric dis- organic phosphonates (e.g., HEDP and PBTC) and
persant and phosphonates, as compared to the bulk- dispersant polymer. For example, if 1 ppm of HEDP
water chemistry. was consumed in the initial phase of deposit forma-

3

Figure 3 — Water analyses from a PCT test using an
All-Organic program; standard make-up water, 2-5
cycles of concentration, 35°C return temperature.
Polymer consumption is related to the Mg-Ca
concentration cycle split (PCT Test 5).
tion, this represents 24% of the total HEDP in the
bulk water. However, only a very small percentage of
calcium (0.8%) and alkalinity (1.2%) from the bulk
water would be consumed during the formation of that
same deposit. Based on the magnitude of these
changes, measurement of HEDP or polymer consump-
tion is analytically more feasible than measurement
of calcium or alkalinity consumption. This also indi-
cates that consumption of the actives is a sensitive
indicator of the formation of deposits.
In PCT Test 5 (an All-Organic treatment program at
pH 9), the conductivity was increased incrementally,
thus increasing the concentration cycles. Magnesium
cycles remained at theoretical levels, but calcium pre-
cipitated. Results in Figure 3 show the loss of dis-
persant polymer as calcium carbonate precipitates.
The X-axis is “Delta Cycles” or “Cycle Splits”, defined
as the difference in Mg and Ca concentration cycles.
The farther out of balance the program operates, the
greater the actives consumption. Thus if we can mea-
sure the actives consumption and provide a corrective
action to the system, we should be able to improve
performance of the cooling water system.
MEASUREMENT OF ACTIVE POLYMER
When treatment actives analyses are used in conjunc-
tion with inert tracers (for control of treatment
dosage), it is essential that accurate measurement
methods for treatment actives be used. Inaccurate
analysis of treatment actives can lead to serious mis-
interpretation and response to system stresses and
performance problems. Historically, it has been very
difficult to provide an accurate, general analysis of
polymeric dispersants.17 Existing polymer analysis
4
methods have suffered from one or more of the fol-
lowing problems:18–21
(1) complicated methods requiring separation, extrac-
tion, and/or adsorption/washing to remove the
polymer from the sample matrix
(2) complicated analysis methods with long time
period for development of test response (e.g.,
15 minutes for Hyamine turbidity test)
(3) interferences that give false-positive response
(indicating polymer is present at a significant
level, when it is not)
(4) subjective analysis based on visual comparisons
(5) limited dynamic range of polymer levels that re-
quire extra steps for sample dilution or prepara-
tion to measure low or high dosages
(6) complicated statistical analysis and equipment
calibration procedures that require extensive
number of samples to help reduce interferences
In order to address all of these needs, a new active
polymer test method has been developed for measure-
ment of polymeric scale inhibitors/ dispersants in
water systems.22–25 The new analysis method is used
for grab sample testing and can be measured by fluo-
rescence or colorimetric techniques. The new active
polymer test method (grab samples) also complements
the on-line monitoring/control capabilities of a new
generation of fluorescent tagged polymers, which are
subsequently described in this paper. The new active
polymer test method addresses application needs on
the lower-half of the diagram describing system moni-
toring/control hierarchy (Figure 4), whereas the new
generation of fluorescent tagged polymers addresses
needs in the upper-half of Figure 4.
The new active polymer test method utilizes the fol-
lowing grab-sample analysis procedure:
(1) specified amount of dye/buffer reagent is added
to cuvette
Continuous direct control
➞
Computerized indirect control
Improved System Control
Continuous monitoring with periodic control
Computer-aided SPC/Manual adjustment
Trend charts/Control charts/Special cause ID
Regular testing/Data collection/Manual adjustment
Irregular testing frequency/Limited data collection/Irregular adjustment
Figure 4 — Hierarchy of treatment dosage monitoring/
control
(2) defined amount (1 mL) of filtered water sample is in specific applications by changing the ratio of re-
added to reagent solution agent solution to water sample. This new polymer
analysis test provides very linear/predictable re-
(3) after 30 seconds, sample is analyzed (colorimetric
sponse (Figure 5) throughout the 0–20 ppm dosage
or fluorescence methods)
range. The high ppm dosage range can be extended
(4) analyzer readout indicates ppm dosage of active or a high-resolution low polymer dosage can be de-
polymer termined by changing the ratio of reagent solution
volume to water sample volume. Chemical compat-
Polymer consumption and treatment product dosage
ibility guidelines for this new method are listed in
are obtained from inert tracer reading/treatment com-
Table 7. A more extensive list of application guide-
position and comparing those results with active poly-
lines has also been published.
mer remaining in the system (step 4).
Application guidelines (dissolved ions and operating
conditions) for the new active polymer test method is CASE HISTORY
listed in Table 7.22–24 These guidelines can be extended A North American refinery cooling water system was
experiencing high-stress operating conditions due to
very high temperature heat-exchangers. The treat-
Table 7 — Chemical compatibility guidelines for new
active polymer test
ment product was a Stabilized-Phosphate type pro-
gram. Although the treatment program worked in
Preferred Analysis most of the cooling water system, deposit formation
Range *,** was occurring in the high-temperature exchangers.
Alkalinity (HCO3– as CaCO3) 0 – 1,800 mg/L Polymeric dispersant consumption averaged 72%
Calcium (as CaCO3) 0 – 1,700 mg/L (Figure 6), which corresponded to heat exchanger
fouling that was confirmed by visual inspections.
Conductivity 0 – 6,000 µS/cm
Polymer consumption was determined from the poly-
Iron (soluble, as Fe) 0 – 90 mg/L mer dosage added (from inert tracer readings) and
Magnesium (as CaCO3) 0 – 1,700 mg/L the level of active polymer remaining (using the new
Manganese (as Mn) 0 – 860 mg/L Active Polymer Test).
Orthophosphate (as PO4) 0 – 2,100 mg/L A new treatment program was implemented, which
pH 4.5 – 11 included a high-stress polymeric dispersant capable
of operating effectively under high-temperature con-
Silicate (as SiO2) 0 – 530 mg/L
ditions. The polymeric dispersant consumption was
Sodium (as Na) 0 – 2,000 mg/L dramatically reduced (72% –>10%) upon implemen-
Sulfate (as SO4) 0 – 1,700 mg/L tation of the new treatment program, as shown in
Turbidity 0 – 120 NTU Figure 6. The reduction in polymer consumption also
correlated to a significantly reduced level of fouling
**Upper limit of operating range is based on the concentration of in the high-stress heat exchangers.
chemical species required to produce a 10% change in response
of analysis method (using reference dosage of 10 ppm polymer
actives).
** Adjusting ratio of reagent:water sample can be used to extend
upper limit of these guidelines

Figure 6 — Data from case history, a high-stress

Figure 5 — Linearity of response from new active cooling water system. Performance improved as %
polymer test to changes in polymer dosage (0-20 ppm) polymer consumption decreased.

5
Overall benefits of the high-stress polymer program
and the new Active Polymer Test are as follows:
• 3-fold increase in active polymer level for a com-
parable level of polymer added to the system
• Reduced % polymer consumption correlates with
improved results in high-stress exchangers
• % polymer consumption can be used as a very valu-
able indicator of system performance and to opti-
mize system operation
• High-stress polymer program allowed only a light
dusting of easy-to-remove powder to form in high-
stress exchangers
• Significantly improved results were obtained even
though cycles increased from 3.2 –>5.7 (and hold-
ing time increased)
• % polymer consumption increased as short-term
operating stresses increased (hydrocarbon leak and
reduced level of polymer added)
Even with doubling the concentration cycles, a hydro-
carbon leak and 18% reduction in the level of poly-
mer actives added, the high-stress polymer program
had better performance and much lower polymer con-
sumption (<1/2 of polymer consumption in original
treatment program). Use of the Active Polymer Test
method made corroboration of these results easy,
quick, and accurate. The use of % polymer consump-
tion also provides a means to quickly confirm if im-
provements made in the system are being maintained
over long time periods.
USE OF FLUORESCENT POLYMERS
The new Active Polymer test method provides an easy,
quick and accurate method to determine polymer con-
sumption. However, the current method was not
developed to be an on-line method. In order to use
polymer consumption as a way to continuously con-
trol a cooling water system, the method must be on-
line. Although it would be possible to automate the
Active Polymer test method, the use of a fluorescent
water-soluble polymer was chosen. The development
of fluorescent water-soluble polymers for use in cool-
ing water systems is known.3,26,27 However, previously
available fluorescent water-soluble polymers did not
meet all the requirements given below.
1. The fluorescent polymer should be similar in struc-
ture and activity to existing polymers used in cool-
ing water systems, since it will replace the current
untagged polymer in cooling water products. The
fluorescence of the polymer must be correlated with
activity.
6
2. The polymer must fluoresce in the visible wave-
length region (λex >370 nm, λem >420 nm) and
the fluorescence of the polymer must be not
interfere with inert fluorescent tracers.
3. The polymer must be stable to oxidizing biocides
at pH between 6.5 and 9, but at least above pH 8.0.
4. The polymer must have stable fluorescence over
the pH range 6.5 – 9.5.
5. The polymer must be stable in cooling water sys-
tems for at least 24 hrs. (hydrolytic stability, ther-
mal stability to 70°C).
6. The fluorescence of the polymer should be free of
interferences under standard cooling water con-
ditions (i.e., Ca, Mg, alkalinity, etc.).
7. The polymer must be capable of being formulated
in products. Some cooling water products are for-
mulated at low pH (1 – 2), while other products
are formulated at high pH (13).
8. The polymer should be photostable and when for-
mulated in products have no undesirable color.
9. Unreacted fluorescent starting material and any
small molecule fluorescent by-products must have
distinct fluorescence properties from the fluores-
cent polymer.
10. The polymer must meet all safety and environ-
mental regulations.
Two general approaches for the synthesis of a fluo-
rescent polymer were considered in the development
of new fluorescent water-soluble polymers (Figure 7).
• Modification of an existing polymer with a fluores-
cent dye after polymerization. This is the method
by which an existing tagged polymer is prepared.3
• Polymerization of the polymer with a small amount
of a fluorescent monomer.
Both methods have been used to prepare fluorescent-
tagged polymers. However, in order to prepare a fluo-
rescent polymer with fluorescence in the visible or
near visible wavelength region (λex >370 nm), the
use of a fluorescent monomer has been more success-
ful. The polymers used in these studies have been
prepared with fluorescent monomers and meet the
requirements given above. In testing a variety of fluo-
rescent polymers, a number of the requirements given
above are worth mention. First, the fluorescent poly-
mer should be similar in activity to the existing dis-
persant polymers used in cooling water systems, since
they will be replacing the existing dispersants. In bench
testing of calcium phosphate dispersancy, tagged dis-
persant polymers were equal to the untagged versions
of the dispersant polymer.
 Postmodification of Existing Polymer
( CH2–CH )x ( CH2–CH )y + z NH2 ⇒ ( CH2–CH )x' ( CH2–CH )y' ( CH2–CH )z'
C=O C=O C=O C=O C=O
F
OH NH2 OH NH2 NH

Copolymerization of Fluorescent Monomer

x CH2= CH + y CH2= CH + z CH2 = CH ⇒ ( CH2–CH )x ( CH2–CH )y ( CH2–CH )z
C=O C=O C=O C=O F
F
OH NH2 OH NH2

Figure 7 — Methods to synthesize a fluorescent-tagged polymer.

Another important requirement was that the poly- forming scale. This is referred to as a concentration
mer needed to have an excitation wavelength above cycle split. To use concentration cycle splits reliably,
370 nm. This made the use of solid-state light-emit- Ca and Mg analyses must be performed on both the
ting diodes (LEDs) and photodiodes possible, thus tower water and the make-up water, for a total of
decreasing the size while increasing the functional- four analyses for each point in time.
ity of the measurement instrumentation. Thus, the
Concentration cycle splits cannot be accurately used
same type of instrumentation described in a previous
if any of the following conditions occur:
paper can be used with these new fluorescent poly-
mers. This was a substantial improvement over • If magnesium silicate formation occurs;
existing fluorescent dispersant polymers.3,26,27
• If the make-up water is variable or there are mul-
Finally, any loss of the fluorescence of the fluores- tiple sources of make-up water;
cent polymer must be related to its activity. Specifi-
• If there are interconnected systems;
cally, laboratory testing showed that pH, oxidizing
biocides or other species present in a cooling water • If there are interferences with the analysis of Ca
system did not affect the fluorescence of the polymer. or Mg; and/or
• If extra Ca is added to the system to increase
METHODS USED TO MONITOR SCALE hardness.
For several years, consumption has been discussed If any of the above circumstances occur, the use of
in relation to the performance of the cooling water concentration cycle splits will not provide meaningful
system.3,13 We believe that the consumption of treat- information on scaling in the cooling water system.
ment actives actually “PRE-cedes” the formation of
In addition, it is not possible to measure Ca and Mg
deposits, and allows one to “PRE-act” by changing
on-line with enough accuracy and precision using
the system operating conditions in order to “PRE-vent”
current technology. Thus, analyses must be done off-
serious performance problems. The increase in poly-
line using grab samples. There will always be a sig-
mer consumption with increasing concentration cycles
nificant lag time between the sampling and analysis
has been demonstrated.3 In addition, polymer con-
time, which could cause difficulties in situations
sumption and fouling monitor friction factors were
where conditions change rapidly. Finally, the analy-
shown to increase in a case history from a chemical
sis of Ca and Mg must be accurate and precise, which
processing plant.3 However, additional experimental
requires analytical laboratory analysis. Because of
information was desirable to determine how the poly-
the time-consuming nature of performing four analy-
mer consumption is related to commonly used methods to
ses, and the need for accuracy and precision, this is
determine the onset of scaling events.
an approach that is best suited for laboratory use.
Several methods are commonly used to determine if
A second method that is useful to show that scaling
scaling is occurring. In All-Organic Programs, which
is occurring is measurement of filtered and unfiltered
consist of organophosphonates, copper corrosion in-
total phosphate, orthophosphate or zinc. This method
hibitors and polymeric dispersants, the difference
is used in stabilized phosphate, alkaline phosphate
between magnesium concentration cycles and calcium
and zinc-containing treatment programs. Again, as
concentration cycles is a good method to determine if
with concentration cycle splits, analytical methods
calcium-containing species are precipitating and
7
Figure 8 — Comparison of scale onset as determined
by concentration cycle splits and heat transfer
resistance. Data from a Pilot Cooling Tower test using
an All-Organic program; standard make-up water,
2-5 cycles of concentration. (PCT Test 6)
used to determine the concentration of total and
orthophosphate and zinc must be sensitive, precise
and accurate. Again, on-line analysis is difficult,
especially considering the need to perform measure-
ments on filtered vs. unfiltered water.
A third method that can be used to show system scal-
ing, regardless of treatment program, is a device to
measure heat transfer resistance (HTR). The unit
used in this work was the DATS™ Fouling Monitor
from Bridger Scientific. This measures the tempera-
ture difference across a heat transfer surface, and
calculates a relative value of the HTR. If insulating
deposits form on the surface, the temperature differ-
ence (and the HTR calculated from it) increases. Foul-
ing monitors provide a reasonable indication of the
fouling of a heat exchanger.28 This measurement is
on-line, uses actual cooling system water, and condi-
tions can be chosen to closely simulate the actual heat
exchange surface conditions. These advantages make
fouling monitors a useful tool.
However, fouling monitors have significant draw-
backs. First, the fouling monitor does not measure
an actual system heat exchanger, but measures a
simulation of the system. It is often difficult to simulate
the actual conditions. For example, fouling monitors
cannot simulate shell-side exchangers. The side-
stream to the unit is often much cooler than the
water in the hottest part of the real exchanger. In
addition, their sensitivity is limited by fluctuations
in the system. Furthermore, they measure fouling
that has already occurred; they cannot be used to
predict that conditions favoring fouling are about to
occur. Finally, fouling monitors are costly, which gen-
erally limits their use to very large cooling systems.
8
Figure 9 — Comparison of scale onset as determined
by concentration cycle splits and polymer con-
sumption. Data from a Pilot Cooling Tower test using
an All-Organic program; standard make-up water,
2-5 cycles of concentration. (PCT Test 6)
USE OF POLYMER CONSUMPTION
IN ALL-ORGANIC TREATMENT
PROGRAMS
Correlation Between Polymer Consumption
and Methods to Monitor Scale — A Pilot Cooling
Tower using an All-Organic treatment program was
set up to compare methods used to indicate scaling
(PCT Test 6). The make-up water used in this test is
given in Table 4. The tower was allowed to cycle up
to beyond 4 cycles where the program is known to
scale in Pilot Cooling Towers. A sample of the cooling
water was collected every hour using an autosampler
and analyzed for Ca and Mg by Atomic Absorption
Spectroscopy. The make-up water was invariant. Note
that the measurement of Ca and Mg could be accom-
plished in the lab, but would be extremely time-con-
suming and expensive to accomplish outside a
research laboratory. The concentration cycle splits
were determined and are shown in Figure 8. Heat
transfer resistance (HTR) from the fouling monitor
was measured and is shown. As seen in Figure 8, the
onset of fouling can be observed as an increase in con-
centration cycle splits, which occurs between Days 2
and 3. However, the onset of scaling, as shown by the
fouling monitor, does not occur until approximately
Day 4. This indicates that, in this test, the concen-
tration cycle splits are a more accurate measure of
the onset of scaling, compared to the heat transfer
resistance.
During the same PCT test (PCT Test 6), the % polymer
consumption was also measured on-line. Figure 9
shows a comparison of the concentration cycle splits
(same data as given in Figure 8) and the % polymer
consumption determined from two fluorometers, using
the equation that follows.
% Polymer Consumption =
Product Dosage (from Inert Tracer) – Fluorescent Polymer
Product Dosage (from Inert Tracer)
x 100
As shown in Figure 9, the % polymer consumption
and the concentration cycle splits (based on Ca and
Mg measurements in the make-up and recirculating
water), track each other very well. Thus, % polymer
consumption can be used as an early indicator that
PRE-cedes the onset of scaling in a cooling water sys-
tem. Additionally, as the % polymer consumption is
determined on-line, it can be used in advanced con-
trol strategies to help prevent problems from occur-
ring. Polymer consumption actually can be a more
sensitive/reliable performance indicator than concen-
tration cycle splits because polymer consumption can
be measured continuously on-line, requires fewer
measurements, and does not require a high level of
consistency in the concentration cycle levels in the
make-up water. As shown in Figure 9, the polymer
consumption consistently trends upward (an indicator
of increase in scaling), before it is clear from the
concentration cycle splits (because there is more
statistical variability) that a change is occurring. So
polymer consumption and concentration cycle splits
are a much more direct indicator of scaling processes
than fouling simulators (e.g., fouling monitor). Since
polymer consumption measurements can be done con-
tinuously on-line with an inert fluorescence tracer and
tagged polymer, this method offers the unique advan-
tage of providing an immediate response to system
changes.
Use of Conductivity to Control Blowdown — The
previous results that measuring on-line polymer con-
sumption provides an excellent warning indicator for
the onset of scaling. Polymer consumption can also
be used to gauge the magnitude of scaling and to
determine that corrective actions have eliminated the
problem. Beyond basic system characterization and
problem-solving, the next step is to provide a higher
level of system control compared to other methods
(e.g., conductivity) using polymer consumption.
In cooling water systems utilizing All-Organic pro-
grams (without pH control), the main control methods
used to prevent scaling are treatment product dos-
age and adjusting concentration cycles through
blowdown. Concentration cycle adjustment has his-
torically been done (sometimes indirectly) using con-
ductivity. Some of the limitations of using conductiv-
ity for cycles control are listed in Table 8. Even if the
recirculating cooling water/make-up water systems
are not impacted by one or more of these limitations,
conductivity does not directly measure scaling pro-
cesses or the scaling tendency of the water. Thus, a
9
Table 8 — Potential limitations of using conductivity
for control of cycles of concentration in cooling water
systems
• No direct measure of scaling tendency
(higher conductivity can occur at lower scaling
tendency and vice versa)
• No direct measure that scaling is occurring
• Conductivity signal is temperature dependent
(temperature coefficient (1-2%/°F or more)
• Temperature coefficient varies based on changes in
water composition
• Fouling of electrodes affects results
• Changes in make-up water composition affects
accuracy of cycles control
• Multiple make-up sources, process leaks, and pH
control acid feed can interfere with accurate measure-
ment of cycles
• “Cycles of conductivity” often does not equal “cycles
of concentration” of dissolved ions (individual or total)
based on interferences listed above
• Can fail destructively (scaling causes reduced con-
ductivity, which causes system to further concentrate
and cause more scaling)
• Conductivity control is often run much lower than
optimum – which leads to inefficient cost/performance
system operation
system using conductivity control may be run ineffi-
ciently or still be subject to scaling even if conductiv-
ity is tightly controlled and the conductivity meter
well maintained.
For example, if the make-up water quality is vari-
able (or any of the other limiting conditions listed in
Table 8 apply), conductivity does not provide as good
a representation regarding concentration cycles of the
cooling tower. Two specific examples of make-up wa-
ter upsets are: (1a-b) increase/decrease in overall con-
ductivity or (2) change in composition of the dissolved
ions. If conductivity control were used under those
conditions, several possible outcomes can occur:
1a. Assume that make-up water conductivity is
600 µS/cm and that conductivity control is used for
setpoint control of blowdown control at 2400 µS/cm
(4 X make-up water conductivity). If the make-
up water conductivity increases from 600 µS/cm
to 1100 µS/cm, then blowdown control will be acti-
vated much sooner (at 2.2 X make-up water con-
ductivity). This will result in larger amounts of
make-up water being used, result in more treated
cooling water being discharged from the system,
and result in inefficient operation and still does
not guarantee that scaling will not be a problem.
Figure 10 — Use of polymer consumption instead of
conductivity to control blowdown. Data from a Pilot
Cooling Tower Test 7 using an All-Organic program;
standard make-up water
1b. Alternatively, assume that make-up water con-
ductivity decreases from 600 µS/cm to 300 µS/cm,
then blowdown control in the example above will
be activated much less often (at 8X make-up water
conductivity). This will result in a significant
increase in holding time index, still not guaran-
tee that a change in conductivity will match a
change in scaling tendencies, and may result in
increased operating costs.
2. A change in chemical composition of make-up
water may or may not coincide with conductivity
changes. For example, the level of magnesium
may decrease and calcium may increase; but the
overall level of conductivity may be unchanged.
In this case, the scaling tendency of the water
increases, even though no apparent change in con-
ductivity control of blowdown would occur. This
can lead to many of the same problems previously
described.
Use of Polymer Consumption to Control Blow-
down — A Pilot Cooling Tower test (PCT test 7) was
used to determine the benefits of polymer consump-
tion control of cycles of concentration, as compared
to conductivity method. In the initial work, concentra-
tion cycles were controlled using conductivity. Scaling
was controlled by maintaining the non-scaling water
chemistry, and the polymer consumption was found
to be approximately 15%.
After testing the operation of the PCT using conduc-
tivity control, the control of the tower was changed
so that the blowdown was controlled by polymer con-
sumption. During this stage of testing, it was demon-
strated that a PCT could be consistently controlled at
a tagged polymer consumption level of 15% (Figure 10),
with good control of scaling. Polymer consumption
10
Figure 11 — Use of polymer consumption instead of
conductivity to control blowdown. Data from a Pilot
Cooling Tower Test 7 using an All-Organic program.
(Make-up water upset condition at about 150 hours.)
was determined using on-line measurement of an
inert fluorescent tracer and a fluorescent tagged dis-
persant polymer. A new controller provided on/off control
of the treatment product feedpump and controlled the
blowdown valve based on polymer consumption.
Figure 11 shows the % polymer consumption and con-
ductivity during an upset in make-up water compo-
sition (after 150 hours elapsed operating time), which
caused an increase in system conductivity. Although
the 2nd make-up water composition (given in Table 4)
contained twice as much calcium, because of the
presence of the more soluble calcium sulfate, the
amount of CaCO3 precipitated may be less. The new
controller maintained the polymer consumption at a
constant level and prevented any scaling increase,
but allowed the tower to operate more efficiently at a
higher level of cooling water conductivity.
The results above were corroborated by concentra-
tion cycle splits, which showed no change after the
upset in make-up water composition occurred. The
predicted effects of using conductivity control in this
upset condition of make-up water composition were
corroborated in additional PCT testing. When the
cooling tower blowdown was controlled by conductiv-
ity, the upset in make-up water composition resulted
in a much greater level of blowdown, and increased
system operating costs with no guarantee that scal-
ing was being prevented. A comparison of the blow-
down rates and make-up rates required during the
make-up water upset under consumption control and
under conductivity control are given in Table 9. Using
polymer consumption to control blowdown and cycles
of concentration, blowdown, make-up water usage,
and associated system operating costs were reduced
compared to using conductivity control.
Table 9 — Comparison of cooling tower operation
under consumption and conductivity control during
a make-up water upset (PCT test 7)
Blowdown Make-Up Water
Control Method Rate (gal/day) Rate (gal/day)
Polymer Consumption 10.2 34.7
Conductivity 24.5 49.0
USE OF POLYMER CONSUMPTION
IN STABILIZED PHOSPHATE
TREATMENT PROGRAMS
Many other cooling water treatment programs use
acid feed and blowdown to control scaling. Work was
also done to determine the feasibility of using polymer
consumption in systems operating under these program
guidelines. As an example, the use of polymer con-
sumption to control concentration cycles and prevent
scale/deposit formation in a Stabilized Phosphate
program will be described. The Stabilized Phosphate
program operates at pH 6.8–7.4 with sulfuric acid
feed. This pH reduces the potential for scale forma-
tion. However, there is greater potential for corrosion.
A mixture of orthophosphate and pyrophosphate
inhibits ferrous metal corrosion. A dispersant poly-
mer prevents calcium phosphate deposits.
CORRELATION BETWEEN POLYMER
CONSUMPTION AND METHODS TO
MONITOR SCALE
PCT tests (PCT Test 8) were also performed using a
stabilized phosphate program to control corrosion and
scaling. Initial tests were done under conductivity
control with pH controlled at 7.0. During this test,
there was very little scale formation observed on the
heat exchanger tubes, and polymer consumption was
very low (<5% polymer consumption). In addition, phos-
phate consumption and filtered/unfiltered splits were
also near zero. The conditions were 750–800 mg/L Ca
(as CaCO3), 375–400 mg/L Mg (as CaCO3), 9/12 mg/L
phosphate (ortho/total as PO4) and polymer levels of
7–9 mg/L. Figure 12 shows what happened when the
pH was increased from 7.0 up to 7.8 under conductiv-
ity control, simulating a loss of acid feed. As the pH
rose, inert tracer readings remained constant, but the
tagged polymer readings began to drop rapidly. This
was not due to a change in the fluorescent properties
of the polymer with pH. Polymer consumption was as
high as 30%. Heat exchanger fouling, as measured by
HTR, began to increase about eight hours later. The
next morning, there was a very slight, barely percep-
tible, dusting of white material on the hottest tubes.
Filtered/ unfiltered phosphate splits increased to 1.1–1.5
ppm, still below the “standard” 2 mg/L.
11
Figure 12 — Comparison of scale onset as determined
by heat transfer resistance and polymer consumption.
Data from PCT Test 8 using a Stabilized Phosphate
program (pH upset condition); standard make-up
water, 4-5 cycles of concentration.
Polymer consumption was by far the most sensitive
indicator of the performance problem. The deposit on
the heat exchanger tube was difficult to see visually
without an intense light source illuminating the tube
surface. The HTR increased, but the actual change
was very small (0.3E-5). As a practical matter, no one
would believe such an increase was real unless it con-
tinued for several days. Phosphate splits also indi-
cated a possible problem. However, field practice is
to keep the unfiltered minus filtered phosphate dif-
ference less than 2 mg/L. The 1.5 mg/L difference in
orthophosphate observed in this test might not be
enough to indicate a serious cause for concern. By
the time the problem would have been detected by
“traditional” methods, a significant amount of scale
would have already been built up. A few such upsets
per year would lead to heavy scale over time.
At approximately hour 20, acid was fed to return the
pH to 7.0. This restored the program to normal con-
ditions within a few days, as noted by the return to
near zero phosphate splits. Although the rate of
increase in HTR dropped substantially, the HTR was
still higher than the initial HTR, indicating that the
heat exchanger still had some fouling. This was also
confirmed visually. Reducing the tower pH to 6.5 had
very little additional effect.
Thus, there is a good correlation between the onset
of scaling and an increase in the % polymer consump-
tion. The other methods used to determine the onset
of scaling are either not sensitive enough to use or
are not easily amenable to use on-line as polymer
consumption.
USE OF POLYMER CONSUMPTION TO
CONTROL BLOWDOWN
A demonstration of the use of polymer consumption
to control blowdown in a Stabilized Phosphate pro-
Figure 13 — Comparison of scale onset as determined by heat transfer resistance and
polymer consumption in PCT Test 10 during iron upsets using a stabilized phosphate
treatment program; pH = 7; standard make-up water, 4-5 cycles of concentration
A. Under Conductivity Control
gram was performed (PCT Test 9). When a loss of
acid feed occurred in the test using polymer consump-
tion to control blowdown, the new controller responded
to the pH upset by initiating blowdown, thus reduc-
ing the cycles of concentration. Phosphate splits
remained small and scale control was maintained.
Even more advanced forms of system control could
be implemented by inputting additional signals (such
as pH) from the system to provide more detailed prob-
lem-solving and also additional automatic corrective
actions (e.g., activating a 2nd acid feedpump to com-
pensate for the loss of acid feed).
Since Stabilized Phosphate programs utilize acid feed
and operate at a lower pH than other treatment pro-
grams, corrosion and iron upsets can also occur. An iron
upset would result in fouling of the heat exchanger,
but no change in the conductivity of the cooling sys-
tem. In another PCT test (PCT Test 10), an iron upset
was initiated by feeding an iron-containing solution
directly into the basin to represent the upset condition.
When conductivity was used to maintain cycles of
concentration, only about 50% of the added iron was
recovered in the recirculating water. The fouling moni-
tor on the system showed an increase in HTR (heat-
transfer resistance on the heat-exchanger tube) and
deposits were visually observed (Figure 13A). At the
same time, a 10–20% increase in polymer consump-
tion indicated that an increase in scaling/deposition
was occurring. Even losses of 0.5 mg/L of iron or less
were readily detectable using polymer consumption
methods in this PCT test, which shows the high sensi-
tivity of polymer consumption method as a monitor of
system performance. When the iron upset was repeated
under polymer consumption control (Figure 13B), the
12
new controller responded as expected by increasing
blowdown rate. This action helped prevent scaling/
deposit formation in the system (no increase in HTR)
and maintained the polymer consumption level until
the upset condition was corrected.
The ability of a new controller to provide on/off con-
trol of treatment product feedpump and the blowdown
valve was demonstrated. Also, the ability of the new
controller to respond to severe upset conditions (loss
of acid feed and iron upset) was demonstrated. Under
normal conditions, polymer consumption-based con-
trol of blowdown allowed operation of the cooling
water system at higher cycles than usually encoun-
tered, while still minimizing scale formation. This
allowed system performance to be maintained while
reducing overall operating costs due to increased
cycles of concentration and reduced blowdown rate.
When an upset condition occurred, the new controller
responded by increasing blowdown rate. This action
helped prevent scaling/deposit formation in the sys-
tem until the upset conditions could be corrected.
CONCLUSIONS
1. The measurement of on-line polymer consumption
and concentration cycle splits are direct indicators
of scaling processes and are more sensitive indica-
tors of scaling processes than fouling simulators
(e.g., fouling monitors).
2. Since polymer consumption measurements can be
done continuously on-line with an inert fluores-
cence tracer and tagged polymer, this method
offers the unique advantage of providing an
immediate response to system changes.
3. It has been demonstrated that the dispersant
polymer in cooling water treatment programs is
consumed by scaling events and several types of
active treatment components are present at
enriched levels in deposits.
4. The farther out of cycle balance the program oper-
ates, the greater the actives consumption.
5. A new rapid and easy colorimetric test was devel-
oped to measure the amount of active polymer.
Polymer consumption, as measured by the new
test, can be used as a very valuable indicator of
system performance and for overall optimization
of system operation.
6. The development of a new fluorometric dispersant
polymer using a new fluorescent tag makes it fea-
sible to measure polymer actives online without
reagents.
7. Polymer consumption was used as the basis for
blowdown control in both All-Organic and Stabi-
lized Phosphate programs. This control was shown
to save water under normal conditions and mini-
mize scale under upset conditions.
REFERENCES
1. J. E. Hoots, “Methods for Improving Performance
of Water Treatment Programs in Cooling Sys-
tems,” International Association of Corrosion
Engineers, Calgary, Alberta (Canada), 1999.
2. J. C. Horne, N. M. Rao, J. E. Hoots, “Develop-
ment of a Mechanistic Understanding of Aromatic
Triazole Consumption in Cooling Water,” Official
Proceedings - 60th International Water Confer-
ence, 303-311, 1999.
3. J. E. Hoots, “Water Treatment Dosage Control
and Relationship to Performance,” CORROSION/
95, Paper No. 260, National Association of Corro-
sion Engineers, Houston, Texas, 1995.
4. S. J. Armitage, E. W. Ekis, J. E. Hoots, J. M.
Johnston, “Actives-Based Chemical Control for
Recirculating Cooling Water Systems,” Official
Proceedings - 56th International Water Confer-
ence, 37-43, 1995.
5. S. J. Armitage, J. E. Hoots, “New Methods for
On-Line Monitoring/Control of Corrosion Inhibi-
tors & Performance Relationships,” Proceedings
of the 8th European Symposium on Corrosion
Inhibitors (8 SEIC), Vol. 1, p. 533, 1995.
13
6. S. J. Armitage, J. E. Hoots, “Problem-Solving
Tools for Improved Performance of Treatment
Programs in Cooling Water Systems,” Official Pro-
ceedings – 57th International Water Conference,
Paper No. IWC-96-5, 1996.
7. J. E. Hoots, B. E. Moriarty, B. F. Pesigan, J. P.
Rasimas, “Latest Methods of Performance Opti-
mization and Control in Cooling Water,” CORRO-
SION/2001, National Association of Corrosion
Engineers, Houston, Texas, 2001.
8. P. R. Puckorius, S. D. Strauss, “Special Report –
Cooling Water Treatment,” Power, 139, No. 5,
p. 17, 1995.
9. Air Force Civil Engineering Support Agency,
“Industrial Water Treatment Primer,” U.S.
Department of Commerce, Publication ADA 262
698, March 1, 1992.
10. K. P. Fivizzani, R. W. Cloud, J. E. Hoots, “Influ-
ence of Mechanistic Studies on the Development
of New Cooling Water Programs,” CORROSION/
89, Paper No. 175, National Association of Corro-
sion Engineers, Houston, Texas, 1989.
11. U.S. Patent 5,171,450 (assigned to Nalco Chemi-
cal Company), J. E. Hoots, December 15, 1992.
12. U.S. Patent 5,435,969 (assigned to Nalco Chemi-
cal Company), J. E. Hoots, M. R. Godfrey, July
25, 1995.
13. J. E. Hoots, D. A. Johnson, J. D. Lammering, D.
A. Meier, B. Yang, “High Cycle Cooling Tower
Operation: Hurdles and Solutions,” 60th Inter-
national Water Conference, Paper No. IWC-99-
48, 1999.
14. Z. Amjad, “Factors to Consider in Selecting a Dis-
persant for Industrial Water Systems,” Ultrapure
Water, Vol. 16(7), 17,18,20,22-24, 1999.
15. Ondeo Nalco Company, “Ondeo Nalco High Stress
Polymer,” Bulletin 425, 1999, and “Ondeo Nalco
High Stress Polymer improves performance of
A-Z-Lite program in heat stressed system,” Case
Study CH-438, 1999.
16. J. E. Hoots, G. A. Crucil, “Role of Polymers in the
Mechanisms and Performance of Alkaline Cool-
ing Water Programs,” CORROSION/86, Paper
No. 13, National Association of Corrosion Engi-
neers, Houston, Texas, 1986.
17. Hach Water Analysis Handbook, “Polyacrylic
Acid: Absorption-Colorimetric Method, Method
8107,” 3rd Edition, 1059, 1997.
18. J. Richardson, M. G. Trulear, “Monitoring and
Control of Polymeric Scale Inhibitors,” American
Chemical Society (Book of Abstracts), 218th ACS
National Meeting, COLL 226, 1999.
19. W. M. Hann, T. W. Sanders, N. Pugliano, “Adsorp-
tion Studies of Tagged Polyelectrolytes on Crys-
tal Surfaces: Industrial Implications,” American
Chemical Society (Book of Abstracts), 218th ACS
National Meeting, COLL 228, 1999.
20. S. Patel, P. J. Sullivan, F. O’Brien, M. T. Muldoon,
D. V. Onisk, J. W. Stave, “Is There Enough Poly-
mer in the Tower,” CORROSION/2000, Paper No.
329, National Association of Corrosion Engineers,
Houston, Texas, 2000.
21. W. A. Mitchell, G. A. Small, M. A. Reinsalu, D. O.
Veil, “The Use of Novel Monitoring and Control
Technology in Cooling Water Systems to Lower
Operating Costs,” CORROSION/95, Paper No.
263, National Association of Corrosion Engineers,
Houston, Texas, 2000.
22. U.S. Patent 5,389,548 (assigned to Nalco Chemi-
cal Company), J. E. Hoots, C. C. Pierce, M. R. R.
W. Kugel, Feb. 14, 1995.
23. Ondeo Nalco Company, “Ondeo Nalco Active
Polymer Test – DR/2010 Procedure,” Analytical
Procedure (AP-116/2010), 1999.
24. Ondeo Nalco Company, “Ondeo Nalco Active
Polymer Test – DR/890 Procedure,” Analytical
Procedure (AP-116/890), 1999.
25. Ondeo Nalco Company, “Ondeo Nalco Active
Polymer Test – Pocket Colorimeter Procedure,”
Analytical Procedure (AP-116/PC), 2000.
26. U.S. Patent 5,635,575 (assigned to Kurita Water
Industries, Ltd.), M. Kira, N. Kobayashi, June 3,
1997.
27. U.S. Patent 5,948,268 (assigned to Nippon
Shokubai Co., Ltd. and Kurita Water Industries,
Ltd.), S. Yamaguchi, T. Fujisawa, Sep. 7, 1999.
28. P. J. Sullivan and J. F. Garey,” Effectiveness of
Polymer Phosphonate Blends for Inhibition of
CaCO 3 Scale,” Industrial Water Treatment,
December 1996.

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