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Carbosperse K-700
Water Treatment Polymers
2010, The Lubrizol Corporation. All rights reserved.
Abstract
Controlling silica-silicate fouling in industrial water systems operating with high silica containing
feed waters is very challenging and requires non-conventional deposit control agents. Several
laboratory evaluations were conducted to better understand the performance of a new
polymeric silica-silicate deposit control agent. The suitability of the new polymer for use in high
temperature applications as silica polymerization inhibitor and particulate dispersant (e.g.,
silica, magnesium silicate, iron oxide, clay) is evaluated by efficacy testing after polymer
exposure to thermal stress.
Keywords: silica polymerization, inhibition, particulate matter, iron oxide, clay, silica,
magnesium silicate, dispersion, fouling, thermal stability.
Introduction
Silica and silicate-based scaling that occurs in industrial water systems associated with the use
of silica-laden feed waters poses significant technical and operational challenges. The
systems affected by silica and silicate-based systems include cooling, reverse osmosis (RO)
process, and geothermal. The commonly occurring scales are amorphous silica, calcium
silicate, magnesium silicate, iron silicate, etc. These deposits generally accumulate on RO
membrane and heat exchanger surfaces, pipes, pumps, and other equipment surfaces
reducing heat transfer and RO membrane performance as well as causing increased operating
costs, premature equipment replacement, etc.
In evaporative cooling systems, water technologists must maintain silica at acceptable levels
(usually <180 mg/L in absence of silica/-silicate control agents) to avoid the formation silicabased deposits. This requires (a) operating systems at low cycles of concentration which
increases water consumption and/or (b) the incorporation of silica-silicate control agents in the
water treatment programs. In geothermal applications, silica-scale formation typically occurs
when brine is cooled in the course of brine handling and energy extraction. Factors
contributing to of silica-based deposits include variable fluid compositions, fluctuating plant
operating conditions, and the complex nature of silica polymerization reaction collectively
contribute to silica-silicate fouling problem. The composition and the amount of silica scale as
well as the rate at which it forms is dependent upon factors including mineral concentration of
feed water, pH, temperature, flow velocity, metallurgy, and system pressure.1,2
Once formed, silica-silicate based deposits are particularly difficult to remove from industrial
water systems. Both chemical and mechanical methods are used to remove silica-silicate
based deposits. However, strong chemical cleaners (e.g., ammonium bifluoride, hydrofluoric
acid) pose environmental challenges and require care to avoid damaging equipment whereas
mechanical cleaning is labor intensive.
Over the years, a variety of approaches have been proposed to combat silica-silicate fouling in
industrial water systems. These methods fall into six (6) categories:
1) Operating systems at low silica-silicate supersaturation.
2) Reducing silica concentration by precipitation processes in feed water.
3) Using additive(s) to prevent silica polymerization.
4) Inhibiting metal-silicate precipitation.
1/16
systems. Gill and coworkers,11 in a study conducted using high silica water at above pH 9,
documented that a blend of phosphonate and a copolymer of acrylic acid and 2-acrylamido-2methyl propane sulfonic acid can effectively extend the operating limits for silica from 120 to
300 mg/L.
The suitability of the silica-silicate deposit control agents for use in high temperature
applications is also of importance to water technologists. The effect of heat treatment on
polymer performance as a scale inhibitor and dispersant has been the subject of numerous
investigations. However, there is relatively little practical information available to water
treatment technologists pertaining to the thermal stability of low MW polymers used in high
temperature applications. Polymers used in high temperature applications should be able to
sustain performance where exposed to high temperature and pressure environments
associated with boiler and thermal desalination processes. McGaugh and Kottle12 studied the
thermal degradation of P-AA and later the thermal degradation of an acrylic acid-ethylene copolymer. They used infrared and mass spectrographic analysis to examine the degradation
processes that occurred in several temperature regions: 25 to 150C, 150 to 275C, 275 to
350C, and above 350C. Their results in air (minimal heating) suggest that dry P-AA
decomposes by forming an anhydride, probably a six-member glutaric anhydride-type structure
at temperature up to 150C. At 350C there is drastic un-measurable change and strong unsaturation absorption. Mass spectrographic analysis showed that carbon dioxide was the
major volatile product at 350C.
Masler13 investigated the thermal stability of several homopolymers [i.e., polyacrylic acids
(PAAs), polymethacrylic acids (PMAAs), polymaleic acid (PMAs)] used for deposit control in
boiler water treatment applications. It was demonstrated that under the experimental
conditions employed (pH 10.5, 250C, 18 hr) that PAA, PMAA, and PMA all underwent some
degradation. In terms of molecular weight (MW) loss, PMAA lost slightly less MW than PAA
which lost considerably less than PMA.
Additionally, PAA and PMAA had minimal
performance changes whereas PMA displayed a substantial loss in performance.
Several years later, Zuhl and Amjad14 using a similar test method showed that polymer
performance as dispersants of hydroxyapatite and iron oxide is affected both by temperature
level and exposure time. More recently, Amjad and Zuhl15 reported that heat treatment has a
significant effect on a polymers inhibitory properties. Heat treatment of co- and ter-polymers
has been shown to cause (a) a decrease calcium phosphate inhibition and (b) a slight increase
calcium carbonate inhibition. It is generally understood that exposing deposit control polymers
to thermal stress causes varying degrees of performance loss depending up the temperature,
exposure time, pH, concentrations, and the presence of oxidizing agents.
Although, the mechanisms of silica-silicate inhibition, deposition, dispersion, etc., have been
studied in great depth, no unified understanding of various processes involved in silica-silicate
deposition has been fully developed. In previous papers, we reported the results of laboratory
experiments designed to determine the efficacy of various commercially available polymeric
additives touted as silica polymerization inhibitors and metal-silicate dispersants.16 It was
shown that acrylic acid based homo- and co-polymers commonly used as deposit control
agents are ineffective as silica polymerization inhibitors. The results of earlier studies also
reveal that low level of metal ions (e.g., Al, Fe, cationic polymeric flocculant) exhibit marked
adverse effects on silica inhibiting polymer performance.17
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It is generally accepted that lowest limit of amorphous silica saturation level in industrial water
systems is 1.2x. Based on the previously published data, it can be assumed that a
conservative maximum treated silica saturation level in cooling water systems is 2.2x. In the
present study, for the purposes of evaluating silica polymerization inhibitors, we selected a
more challenging water chemistry with a silica saturation level extended to 3.0x.
The present study is primarily concerned with the thermal stability of commercially available
silica-silicate deposit control agents. Polymers were exposed to high temperatures (i.e., 110 to
300C) and then evaluated for their efficacy as silica polymerization inhibitors and particulate
(e.g., silica, magnesium silicate, iron oxide, and kaolin clay) dispersants. It is hoped that the
data presented in this paper will enable the water technologists to select polymers that meet
treatment program objectives for systems operating under stressed conditions (high pH, high
temperature, high silica supersaturation, etc.).
Experimental
Reagent grade chemicals and distilled water were used throughout the study. Silica stock
solutions were prepared from sodium metasilicate, standardized spectrophotometrically, and
stored in polyethylene bottles. Calcium chloride and magnesium chloride solutions were
prepared from calcium chloride dihydrate and magnesium chloride hexahydrate, and were
standardized by titrating with standard ethylenediammine tetraacetic acid.
Table 1 summarizes the descriptions, compositions, and acronyms of the polymeric
commercially available additives evaluated in the present study including a new proprietary
copolymer blend (CP7 or Carbosperse K-XP229 copolymer). The results herein are
reported on a 100% active inhibitor basis.
Polymer Heat Treatment
Polymer solutions were prepared containing 10% polymer (as active solids) at pH 10.5 using
sodium hydroxide to neutralize the polymer. Sodium sulfite was added as an oxygen
scavenger. A known amount of polymer solution was retained for characterization and
performance testing. The balance was charged to a stainless steel tube. The headspace was
purged with nitrogen followed by tightening the fittings. The tube was then placed in the oven
maintained at the required temperature [either 110C (35.5 psig), 150C (84 psig), 200C
(241 psig), 250C (390 psig), or 300C (1,271 psig)]. After 20 hr, tubes were removed from the
oven, cooled to room temperature, and the solutions transferred to vials for characterization
and performance testing.
Silica Polymerization Inhibition Test Method
Reagent grade chemicals and distilled water were used in accordance with Lubrizols Silica
Polymerization Inhibition Test Procedure,18 schematically shown and discussed below.
4/16
Adjust to
pH 7.0
Sample and
Filter through 0.22 micron
+ Calcium and
Magnesium
Solution
Re-Adjust to
pH 7.0
Analyze
for SiO2
Silica polymerization experiments were performed in polyethylene containers placed in doublewalled glass cells maintained at 40C. The supersaturated solutions were prepared by adding
known volumes of stock solution of sodium silicate (expressed as SiO2) solution and water in
polyethylene containers. After allowing the temperature to equilibrate, the silicate solutions
were quickly adjusted to pH 7.0 using dilute hydrochloric acid [HCl]. The pH of the solutions
was monitored using Brinkmann/Metrohm pH meter equipped with a combination electrode.
The electrode was calibrated before each experiment with standard buffers. After pH
adjustment, a known volume of calcium chloride and magnesium chloride stock solution was
added to the silicate solutions. The supersaturated silicate solutions were re-adjusted to
pH 7.0 with dilute HCl and/or NaOH and maintained constant throughout the silica
polymerization experiments.
Experiments involving inhibitors were performed by adding inhibitor solutions to the silicate
solutions before adding the calcium chloride and magnesium chloride solution. The reaction
containers were capped and kept at constant temperature and pH during the experiments.
Silicate polymerization in these supersaturated solutions was monitored by analyzing the
aliquots of the filtrate from 0.22-m filter paper for soluble silica using the standard colorimetric
method.18 The silicate polymerization inhibition values were calculated according to the
following equation:
[SiO2] sample --[SiO2] blank
%SI =
------------------------------------------- x 100%
[SiO2] initial
--[SiO2] blank
Where:
SI
[SiO2] sample
[SiO2] blank
[SiO2] initial
=
=
=
=
15 ppm
14%
Poor
25 ppm
52%
Fair
50 ppm
84%
Excellent
>75 ppm
>90%
Excellent
cooling water systems were silica and/or silicate deposit may occur. In an earlier paper,19 we
reported the effects of thermal treatment (i.e., a variable temperature [150, 200, and 230C],
pH 10.5, and 20 hr) on the silica polymerization inhibition performance of the polymers herein
designated as P3, CP3, CP5, and CP6. The results of that study clearly show that the
polyacrylate (P3) and copolymers CP3 and CP5 (promoted as silica-silicate deposit control
agents) performed poorly (<5% inhibition) as silica polymerization inhibitors when exposed to
150 and 200C whereas CP6 retained >95% of is performance (vs. no thermal stress).
In this study, to understand the impact of thermal treatment on the performance of CP7 as well
as the other polymers discussed, we conducted a series of experiments involving exposing the
polymer to thermal stress (variable temperature [200, 230, 250, and 300C], pH 10.5, and 20
hr) before evaluating the silica polymerization inhibitor performance. Figure 2 presents
comparative silica polymerization inhibition data before and after thermal stress at 50 ppm
polymer dosages.
Figure 2 silica polymerization inhibition data for polymers in the absence of thermal stress
show that the copolymer blends (i.e., CP6 & CP7) are effective but the other polymers
evaluated are ineffective inhibitors under the high silica saturation level (3.0x) test conditions.
More specifically the %SI values obtained for the homo- (i.e., P1 & P3) and copolymers (i.e.,
CP2, CP3, & CP5) are <20% compared to >80% obtained for the copolymer blends (CP6 &
CP7). These data clearly show that the deposit control polymers containing greater than 50%
carboxylic acid monomer groups (i.e., P1, P2, CP2, CP3, & CP5) exhibit poor performance as
silica polymerization inhibitors. By contrast, the copolymer blends (CP6 and CP7) that contain
less than 50% carboxylic acid monomer groups are significantly better silica polymerization
inhibitors and a significant improvement over current silica inhibitor technology.
Figure 2 silica inhibition data for polymers after thermal stress indicate the following:
1) The homopolymers (P1 & P3) and copolymers (CP2, CP3, & CP5) are ineffective (<10%)
silica polymerization inhibitors.
2) The two copolymer blends (CP6 & CP7) are very effective (80%) silica polymerization
inhibitors after thermal stress at 200C.
3) Thermal stress above 230C for CP6 causes a significant reduction performance.
4) Thermal stress above 250C for CP7 causes a reduction in performance. However, the
silica polymerization inhibition values for CP7 after thermal stress at 250 and 300C were
greater than 70% and greater than 60%, respectively.
Figure 3 takes a closer look at the silica polymerization inhibition performance of CP6 and CP7
after thermal stress as a function of polymer dosage in the range of 10 to 50 ppm. The post
thermal stress results shown in Figure 3 indicate that (a) both CP6 and CP7 experience a
modest (<15%) performance reduction (suggesting some degradation of the polymer functional
groups) and (b) CP7 is a more effective silica polymerization inhibitor than CP6 at lower
dosages both before and after thermal stress. Collectively, the results discussed above and
data shown in Figures 2 clearly show that CP7 is a superior silica polymerization inhibitor over
a wide range of dosages and after thermal stress. Thus, CP7 because of its superior thermal
stability at high temperature may be a suitable candidate for high temperature silica control
applications.
7/16
8/16
Figure 5 presents magnesium silicate dispersion data collected under standard test conditions
for various polymers (e.g., 2.5 ppm polymer dosages) both before and after exposure to
thermal stress. The data in the absence of thermal stress (at 23C) indicate magnesium
silicate dispersion performance varies with polymer architecture. Furthermore, the new silicasilicate deposit control agent (CP7) provides the best magnesium silicate dispersion among
the copolymers tested which in order of performance (highest to lowest) were as follows:
CP7 > CP2 > CP1 > CP3 > CP6 > CP5.
The impact of thermal stress on the performance of polymers as magnesium silicate
dispersants was investigated. Figure 5 presents comparative performance data. Observations
include:
1) All polymers lose efficacy to varying degrees as magnesium silicate dispersants as the
thermal stress increases from 110 to 250C.
2) CP5 provides the lowest performance before and after exposure to thermal stress.
3) CP3 and CP5 (copolymers promoted as silica-silicate deposit control agents) experience
the greatest performance loss when thermal stress increases from 200 to 250C.
4) CP7 provides the best thermal stress tolerance profile among the copolymers tested.
Iron Oxide Dispersion
Figure 6 shows the iron oxide dispersion by several copolymers and copolymer blends both
before and after exposure to thermal stress as determined by a Lubrizols standard test
method (conditions include synthetic water, pH 7.6, 200 ppm iron oxide, 1 ppm dispersant).21
We also evaluated the impact of increasing polymer dosage above 1 ppm. Based on the data
presented in Figure 6 (see 23C @ 1 ppm and 23C @ 2 ppm) and data for other
experiments not shown herein for brevity, we conclude:
1) Polymer performance profiles vary as a function of dosage. As a general rule, polymer
type and architecture are the most significant factors impacting performance with the
greatest performance increases occurring when dosages are increased from 1 to 2 ppm
and incremental if any performance improvements with dosage increases above 2 ppm.
2) All copolymers except CP5 and CP1 provide greater than 70% dispersion at 1 ppm
dosages.
3) Increasing copolymer dosages from 1 to 2 ppm improves performance to varying degrees.
a) All but CP5 provided excellent (>80%) iron oxide dispersion.
b) CP7 and CP3 display comparable performance and improvement with dosage.
The impact of thermal stability on the polymer performance as iron oxide dispersants was
evaluated by conducting several experiments under similar experimental conditions. Figure 6
also shows the comparative data for polymers after thermal exposure (@ 110, 150, and
200C). It can be seen that all copolymers lose efficacy to varying degrees depending on the
polymer architecture and the thermal treatment. The data indicate that exposing the polymers
to 110C causes insignificant (<10%) iron oxide dispersion performance loss suggesting
minimal degradation of the functional groups and/or the loss in molecular weight. However,
the situation was much different when the polymers were exposed to higher temperatures.
Increasing the thermal stress to 200C causes all the polymers tested to lose some (from 5 to
60%) of their activity as iron oxide dispersants. It is evident CP7 outperformed and is a
significant improvement to all the polymers investigated.
9/16
P. P. Nicholas and Z. Amjad Method for Inhibiting and Deposition of Silica and Silicate
Compounds U. S. Patent No. 5,658,465 (1997).
2.
3.
4.
E. Neofotisou and K. D. Demadis, Use of Antiscalants for Mitigation of Silica Fouling and
Deposition: Fundamentals and Applications in Desalination Systems, Desalination, 167,
257-272 (2004).
5.
6.
7.
8.
L. A. Perez, J. M. Brown, and K. T. Nguyen, Method for Controlling Silica and Water
Soluble Silicate Deposition, U.S. Patent No. 5,256,302 (1993).
11/16
18. Silica Polymerization Inhibition Test Procedure, Lubrizol technical bulletin Silica-PITP,
Oct-2007.
19. Amjad and R. W. Zuhl, An Evaluation of Silica Scale Control Additives for Industrial
Water System, Paper No. 08368, CORROSION/2008, NACE International, Houston, TX
(2008).
20. Z. Amjad and R. W. Zuhl, Laboratory Evaluation of Process Variables Impacting the
Performance of Silica Control Agents in Industrial Water Treatment Programs, AWT
2008 Annual Convention, Austin, TX, November (2008).
21. Z. Amjad, Dispersion of Iron Oxide Particles in Industrial Waters, Tenside Surfactants
and Detergents, 36, 50-56 (1999).
Additive
P-MA
K-732*
K-775*
K-798*
CCP-D**
CCP-A**
K-XP212*
K-XP229*
Acronym
P1
P3
CP1
CP2
CP3
CP5
CP6
CP7
Notes:
MW = Weight average molecular weight.
* Carbosperse K-700 polymer supplied by Lubrizol Advanced Materials, Inc.
** CCP = Competitive copolymer promoted as promoted as silica-silicate deposit control agent.
# Polymer containing >50% carboxylic monomers.
12/16
600
500
400
300
200
100
(550 mg/L silica, 200 mg/L Ca, 120 mg/L Mg, pH 7.0, 40C)
0
0
5
0 ppm
10
15 ppm
Time (hr)
15
25 ppm
20
50 ppm
25
75 ppm
% Silica Inhihition
(550 mg/L silica, 200 mg/L Ca, 120 mg/L Mg, pH 7.0, 40C, 50 ppm polymer)
100
80
23C
200C
230C
250C
60
300C
40
20
P1
P3
CP2
CP3
13/16
CP5
CP6
CP7
100
% Silica Inhibition
CP6 @ 23C
80
CP6 @ 200C
CP7 @ 23C
60
CP7 @ 200C
40
20
0
0
10
15
25
35
50
Polymer Dosage
(600 mg/L SiO2, 105 mg/L Ca, 31 mg/L Mg, 353 mg/L Na, 600 mg/L Ca,
202 mg/L SO4, 58 mg/L HC03, pH 7.6, 1 ppm polymer, 5 hr)
% SiO 2 Dispersed
60
23C
50
110C
40
150C
30
200C
20
250C
10
0
CP1
CP2
CP3
CP5
14/16
CP6
CP7
% MgSiO 3 Dispersed
60
50
23C
40
110C
30
150C
200C
20
250C
10
0
CP1
CP2
CP3
CP5
CP6
CP7
23C @
1 ppm
% Fe 2 03 Dispersed
80
70
23C @
2 ppm
60
110C @
1 ppm
50
40
150C @
1 ppm
30
20
200C @
1 ppm
10
0
CP1
CP2
CP3
CP5
15/16
CP6
CP7
(100 mg/L clay, 105 mg/L Ca, 31 mg/L Mg, 353 mg/L Na, 600 mg/L Cl,
209 mg/L SO4, 116 mg/L HCO3, pH 7.6, 10 mg/L polymer, 3 hr)
80
% Clay Dispersed
70
23C
60
50
110C
40
150C
30
200C
20
10
0
CP1
CP2
CP3
CP5
CP6
CP7
Oct-2010
The information contained herein is believed to be reliable, but no representations, guarantees or warranties of any kind are made to its accuracy, suitability for particular
applications, or the results to be obtained therefrom. The information is based on laboratory work with small-scale equipment and does not necessarily indicate end product
performance. Because of the variations in methods, conditions and equipment used commercially in processing these materials, no warranties or guarantees are made as to the
suitability of the products for the application disclosed. Full-scale testing and field application performances are the responsibility of the user. LUBRIZOL ADVANCED
MATERIALS, INC. shall not be liable for and the customer assumes all risk and liability of any use or handling or any material beyond LUBRIZOLs direct control. The SELLER
MAKES NO WARRANTIES, EXPRESS OR IMPLIED, INCLUDING, BUT NOT LIMITED TO, THE IMPLIED WARRANTIES OF MERCHANT ABILITY AND FITNESS FOR A
PARTICULAR PURPOSE. Nothing contained herein is to be considered as permission, recommendation, nor as an inducement to practice any patented invention without
permission of the patent owner.
Lubrizol Advanced Materials, Inc.
9911 Brecksville Road, Cleveland, OH 44141, P/216-447-5000, F/216-447-5238
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