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Carbosperse™ K-700
Water Treatment Polymers**
In the field of water treatment a variety of additives are incorporated into formulation to
achieve certain desired performance objectives of the industrial water systems. Typical
additives used include polyphosphates, organophosphonates, poly(acrylic acid),
poly(maleic acid), and copolymers containing a variety of functional groups such as
carboxyl, acrylamide, sulfonic acid, ester, etc. The main function of these additives in
the formulation is to prevent the deposition of unwanted deposits (i.e., mineral scales,
corrosion products, biomass, suspended matter, etc.) on equipment surfaces. A variety
of corrosion control additives are also incorporated into water treatment formulations to
control the deterioration of metal – based equipment such as heat exchangers, pipes,
and pumps. Common additives used for corrosion inhibitors include polyphosphates,
organophosphonates, tolyltriazole, and benzotriazole. Furthermore, other additives are
also used to control the formation and deposition of microbiological film on heat
exchangers.1
The type and extent of coagulation/flocculation process for the removal of suspended
matter from surface water has been reported to exhibit a marked antagonistic effect on
the performance of polymers used in cooling water treatment formulations. It has been
shown that the effectiveness of coagulants/flocculants strongly depends on several
parameters including pH, temperature, mixing, and residence time. Chemicals
commonly used as coagulants or flocculants include alum, ferric chloride, and cationic
polymers such as diallyldimethyl ammonium chloride (DADMAC). These chemicals are
known to “carryover” and have been reported to decrease the performance of calcium
phosphate inhibiting polymers.6,7 Thus, the presence of these impurities in the water
may necessitate higher polymer dosage to inhibit scale formation and growth in the
system.
• Type of biocide
• Biocide concentration and application frequency
• Biocide demand
• Contact time
• pH
• Temperature
• Types of organisms present
• Presence of biofilm
• Interaction(s) with other dissolved substances
• Microorgansim loading
• Existing corrosion
Historically, the performance of polymers for mineral scale control in the presence of
soluble and insoluble impurities has been heavily researched. However, the effect of
biocide on the inhibitory activity of polymers commonly used in water treatment
formulations has been mostly overlooked. This paper explores the influence of several
commercial biocides on the inhibitory and dispersancy aspects of several polymers
commonly used in water treatment formulations. The biocides evaluated in this
investigation vary significantly in chemistry ranging from simple molecule to complex
species. It is hoped that the results presented in this paper will help explain why a
specific polymer does not perform as expected, and how polymer dosages can be
adjusted to achieve optimum performance. The polymers and biocides evaluated in the
present study are summarized in Tables 1 and 2, respectively.
Experimental
The polymers and biocides used for this study were selected from commercial
materials. All polymers and biocides solutions were prepared on dry weight basis. The
desired concentrations were obtained by dilution. Stock solutions of calcium chloride
2
and disodium hydrogen phosphate were prepared using distilled water and analyzed for
calcium and phosphate as described previously.2 A Metrohm Brinkmann pH-stat unit
equipped with a combination electrode was used to measure pH. The pH electrode was
calibrated before each experiment with standard buffers. The test solution temperature
was maintained to 50 ± 0.5ºC by passing controlled water through the outer jacket of the
double walled reaction cell.
The sub-saturated calcium phosphate solution was made by the slow addition of the
phosphate stock solution to the desired water. The calcium phosphate inhibitor and
other ionic constituents were added and the solution pH was adjusted if necessary, after
a 30 minutes equilibration period. The calcium stock solution was added, making up the
total volume to 600 mL. In experiments involving the biocide a known amount of biocide
stock solution was added to the test solution following temperature stabilization but prior
to pH adjustment and before the introduction of the calcium solution. For all
experiments, the reaction period was fixed at 20 hours. During each experiment, the
test solution pH was maintained (within ±0.01 pH units) at the desired value using the
pH-stat unit illustrated in Figure 1. Unless specified, the standard test conditions for
calcium phosphate inhibition were 140 mg/L Ca, 9.0 mg/L phosphate, pH 8.50, 50 ºC,
20 hr, and 10 ppm polymer.
Where:
[PO4] exp = phosphate concentration in the filtrate in the presence of the inhibitor at
20 hr.
[PO4] final = phosphate concentration in the filtrate in the absence of inhibitor at
20 hr.
[PO4] initial = phosphate concentration at the beginning of the experiment.
The effect of biocides on the performance of polymers as iron oxide dispersants was
evaluated according to the procedure described previously.9
3
Most commercially available polymers are acrylic acid or maleic acid based homo- and
co-polymers that have been proven to be effective under most typical cooling water
conditions. However, the demands on polymer performance have increased due to
trends towards operating cooling systems under more severe conditions to increase
process efficacy, safety, and water conservation. Additionally, results of recent studies
have shown that the efficacy of these polymers is adversely impacted by the presence
of low levels of impurities commonly encountered in feed streams.6,7,9,10 The following
section present results on the influence of various biocides on the inhibitory power of
several commercially available calcium phosphate inhibiting polymers.
This study evaluated the effects of a variety of commonly used oxidizing and non-
oxidizing biocides as shown below:
Oxidizing Biocides
The results of our testing on oxidizing biocides (Cl2 and Br-Cl) for Polymer B are
presented in Figure 2. The results clearly show no appreciable effect of oxidizing
biocides on polymer performance at the conditions tested (10 to 100 ppm). However, it
is well known that other typical water treatment additives (e.g., azoles, phosphonates,
etc) are susceptible to degradation in the presence of oxidizing biocides. Oxidizing
biocides are also known to increase corrosion and thus the levels of corrosion products
may also increase. Therefore, field applications incorporating both polymers and
oxidizing biocides may have different results as other processes (e.g., corrosion,
precipitation) may occur. The polymers tested in this study, demonstrated resistance to
a loss of performance in the presence of oxidizing biocides.
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Non-Oxidizing Biocides
We also studied the influence of cationic biocides such as THPS (NOxC-1, a positively
charged phosphonium biocide), dialkyldimethyl ammonium chloride [NOxC-2], and
n-alkyldimethyl benzyl ammonium chloride (MW 364 and 351) [NOxC-3 and NOxC-4,
respectively] as a function of concentration on the performance of Polymer B. The
results presented in Figure 4 show that NOxC-1 biocide does not show any antagonistic
effect on the performance of Polymer B. However, the results are markedly different for
the quaternary ammonium compounds (quats) tested.
The use of biodispersants in conjunction with biocides to control the biofilm formation
and deposition of biomass on heat exchanger is well known. In order to understand the
interaction of biodispersants with deposit control polymers, a series of calcium
phosphate inhibition experiments was carried out under standard test conditions. We
evaluated the impact of two (2) biodispersants that contain some charged compounds.
However, non-ionic biodispersants were not included in this study. Figure 7 illustrates
the results of tests on two biodispersants (i.e., NOxBD-1 and NOxBD-2). It is evident
that the presence of biodispersants in calcium phosphate supersaturated solutions has
a marked effect on the performance of polymers.
Figure 7 also shows that the performance of polymers depends upon biodispersant
concentration. For example, at low concentrations (i.e., 1 ppm), both biodispersants do
not exhibit any antagonistic effect on polymer performance. However, increasing the
NOxBD-1 and NOxBD-2 concentration by a factor of 10 results in an approximate 30 to
40% reduction in calcium phosphate inhibition values. It is interesting to note that
NOxC-5 at 0.5 ppm causes a similar dramatic reduction in calcium phosphate inhibition
performance as observed with 10 ppm of NOxBD-1 and NOxBD-2. The results
presented in Figure 7 clearly show that biodispersants also exhibit an antagonistic effect
on polymer performance. In summary, to ensure better overall performance of the
system, factors such as polymer types, polymer–biocide and polymer-biodispersant
interactions, biocide type, and biocide charge should be carefully evaluated in the
selection of formulation additives.
6
The interaction of both oxidizing and non-oxidizing biocides with deposit control
polymers was evaluated by carrying out a series of experiments under standard iron
oxide dispersancy test conditions. Figure 8 details the influence of oxidizing biocides
(Ox-1 and Ox-2) such as chlorine and bromochlorine and four non-oxidizing biocides
(i.e., NOxC-1 to NOxC-4) on the performance of Polymer B. Figure 8 shows the
addition of 0.5 to 5 ppm of oxidizing and non-oxidizing biocides does not show any
significant effect on the performance of Polymer B. Figure 8 also clearly shows that
under the test conditions employed, polymer-biocide interactions do not play a major
role in the overall iron oxide dispersant performance.
Summary
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3. The non-oxidizing biocides that contained no charge group had minimal effect on
calcium phosphate inhibition.
4. Among the non-oxidizing biocides with a positive ionic charge, the quaternary
ammonium-chloride biocides caused significant decreases in polymer performance.
It could not be determined if the type of substitution of the quat (e.g., benzyl or alkyl
groups) made any difference. These positively charged compounds antagonistically
interacted with the anionic polymers.
5. The positively charged phosphonium biocide did not appear to interact with the
inhibition of calcium phosphate.
Acknowledgments
The authors thank The BFGoodrich Company for support to do conduct the studies and
present the results to the AWT 2000 Convention. We also wish to thank our customers
and the biocide suppliers who collectively provided guidance, samples, and ideas that
contributed to this work.
References
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6. L. A. Perez and S. M. Kessler, “Novel Calcium Phosphate Scale Inhibitor,” Chapter
12, Water Soluble Polymers: Solution Properties and Applications, Z. Amjad (Ed.),
Plenum Press, New York, NY (1998).
11. J. Howarth and C. Nalepa, “First Field Trials of Single-Feed Liquid Bromine Biocide
for Cooling Towers,” TP-00-09, The Cooling Technology Institute Annual
Conference, Jan-31 to Feb-3-2000, Houston, TX (2000).
13. S. M. Kessler and K. Given, “Halogen Compatible Treatment Programs for Open
Recirculating Cooling Water Systems,” Paper No. 300, CORROSION/99, NACE
International, Houston, TX (1999).
14. “Legionellosis Guideline: Best Practices for Control of Legionella,” The Cooling
Technology Institute, Houston, TX (Feb-00).
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Table 1
Deposit Control Polymers Evaluated
Figure 1
pH-stat Apparatus Used in Calcium Phosphate Inhibition Experiments
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Table 2
Biocides Evaluated
Br O
H S
NOx-2 Dithiocarbamate Disodium
blend ethylene- H2C N C SNa
bisdithiocarbamate
Salt of dimethyl- H2C N C SNa
dithiocarbamate
H S
0 0
NOx-4 5-Chloro-2-methyl- C C
Isothiazoline 4-isothiazolin-3-one
N CH3 N CH3
blend and S S
2-Methyl-4-isothiazolin-3-one Cl
NO 2
NOx-5 Trisnitromethane Tris
(hydroxymethyl)
HO H 2 C C CH 2 O H
nitromethane
CH 2 O H
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Table 2
Biocides Evaluated (continued)
CH2OH 2
C10H21
12
Figure 2
Effect of Oxidizing Biocides (ppm)
on Calcium Phosphate Inhibition by Polymer B
100
% Ca/P Inhibition
80
60 0
10
40
100
20
0
Ox-1 (Cl) Ox-2 (BrCl)
Oxidizing Biocides
Figure 3
Effect on Non-Oxidizing Biocides (ppm)
on Calcium Phosphate Inhibition by Polymer B
100
% Ca/P Inhibition
80
0
60 5
40 20
50
20
0
NOx-1 NOx-2 NOx-3 NOx-4 NOx-5
Non- Oxidizing Biocides
Figure 4
Effect of Cationic Biocides (ppm)
on Calcium Phosphate Inhibition by Polymer B
% Ca/P Inhibition
100
80 0
60 0.5
40 1
20 2.5
0
NOxC-1 NOxC-2 NOxC-3 NOxC-4
Cationic Biocides
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Figure 5
Effect of NOxC-5 (Poly Quat) on Calcium Phosphate Inhibition
100
% Ca/P Inhibition
80
60
40 Polymer B
Polymer A
20
0
0 0.5 1 1.5 2
Biocide Dosage (ppm)
Figure 6
Effect of NOxC-5 (ppm)
on Calcium Phosphate Inhibition by Various Polymers
100
% Ca/P Inhibition
80
60
0
40 0.5
20
0
Polymer A Polymer B Polymer C Polymer D Polymer E
Polymers
Figure 7
Effect of Biodispersants (ppm)
on Calcium Phosphate Inhibition by Polymer B
% Ca/p Inhibition
100
80
60
0
40
1
20
5
0
NOxBD-1 NOxBD-2
20
Biodispersants
14
Figure 8
Effect of Various Biocides (ppm)
on Iron Oxide Dispersancy by Polymer B
100
% Dispersancy
80
60 0
40 0.5
5
20
0
Ox-1 Ox-2 NOx-1 NOx-2 NOx-3 NOx-4
Biocides
Figure 9
Effect of Cationic Biocides (ppm)
on Iron Oxide Dispersancy by Polymer B
100
% Dispersancy
80
60
0
0.1
40
1
20
0
NOxC-1 NOxC-2 NOxC-3 NOxC-4 NOxC-5 NOxBD-1 NOxBD-2
Cationic Biocides
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For additional technical information pertaining to Lubrizol’s
Carbosperse™ (formerly Good-Rite) K-700 Polymers,
please contact us as follows:
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
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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
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