CA1151498A - Treatment of aqueous systems - Google Patents
Treatment of aqueous systemsInfo
- Publication number
- CA1151498A CA1151498A CA000362311A CA362311A CA1151498A CA 1151498 A CA1151498 A CA 1151498A CA 000362311 A CA000362311 A CA 000362311A CA 362311 A CA362311 A CA 362311A CA 1151498 A CA1151498 A CA 1151498A
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- CA
- Canada
- Prior art keywords
- copolymer
- phosphonate
- polymer
- ppm
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
Abstract
REF. 5722 THE TREATMENT OF AQUEOUS SYSTEMS
Abstract of the Disclosure Sludge is dispersed in cooling water systems by means of a combination of 2-phosphonobutane-1,2,4-tricarboxylic acid and a water soluble organic polymer possessing carboxylic and sulfonate groups.
Abstract of the Disclosure Sludge is dispersed in cooling water systems by means of a combination of 2-phosphonobutane-1,2,4-tricarboxylic acid and a water soluble organic polymer possessing carboxylic and sulfonate groups.
Description
115~4~8 ~ he present invention re~ates to the treatment of aqueous systems, and, more particularly, to reducing or preventing the deposition of solid particles in cooling water systems.
It is well known that particles of solid matter including clay, silt, microbiological debris, ferric oxide and calcium carbonate deposit in aqueous systems and, in particular, in cooling towers and associated equipment.
Such deposits greatly retard the transfer of heat not only by limiting the circulation of water hut by insulating it from the surface it is intended to coo]. A further effect is that serious corrosion may occur under any deposits formed, such corrosion is minimized by keeping the metal surfaces clean. Apart from deposition of hardness salts, particulate matter is introduced into a coolinq system, for example, by the passage of large volumes of air through the cooling tower, and in the process the finely divided solids are effectively scruhbed out of the air.
A similar but even more severe situation exists in cooling and scrubbing the gases formed during steel making where large amounts of ]ime and iron oxide particles are carried over into the aqueous cooling and quenching system. This gives rise to a cooling water which is high in hardness-forming cations and particulate solid levels.
An extremely eficient dispersant is required to operate under these conditions. Accordingly it is highly desirable that some way be found to disperse such particles so as to prevent particle deposition. It is to be appreciated that this is a different problem from the inhibition of scale where certain dissolved salts in the
It is well known that particles of solid matter including clay, silt, microbiological debris, ferric oxide and calcium carbonate deposit in aqueous systems and, in particular, in cooling towers and associated equipment.
Such deposits greatly retard the transfer of heat not only by limiting the circulation of water hut by insulating it from the surface it is intended to coo]. A further effect is that serious corrosion may occur under any deposits formed, such corrosion is minimized by keeping the metal surfaces clean. Apart from deposition of hardness salts, particulate matter is introduced into a coolinq system, for example, by the passage of large volumes of air through the cooling tower, and in the process the finely divided solids are effectively scruhbed out of the air.
A similar but even more severe situation exists in cooling and scrubbing the gases formed during steel making where large amounts of ]ime and iron oxide particles are carried over into the aqueous cooling and quenching system. This gives rise to a cooling water which is high in hardness-forming cations and particulate solid levels.
An extremely eficient dispersant is required to operate under these conditions. Accordingly it is highly desirable that some way be found to disperse such particles so as to prevent particle deposition. It is to be appreciated that this is a different problem from the inhibition of scale where certain dissolved salts in the
- 2 ' ~;
` llS~498 water precipitate or crystallize out or in some cases are deliberately caused to precipitate by the addition of, for example, phosphates and the resulting precipitate or sludge is conditioned so that it can readily be removed rather than adhere to the walls of the vessel.
The use of a variety of polycarboxylates and other low molecular weight polymers, including acrylate polymers, as dispersants in such water systems has been known for many years. It is well recognized, however, that these materials suffer a considerable decrease in effectiveness when used in hard water, for examp]e, water containing more than 300 ppm calcium hardness. This is obviously a serious deficiency in attempting to obtain higher concentration factors in coo]ing systems. The aim of the present invention is to provide a method which is more effective in preventing deposition in hard water than those current]y available.
According to the present invention it has surprisingly been found that this can be achieved hy the use of a specific combination of a specific phosphonate, viz., 2-phosphonobutane-1,2,4-tricarboxylic acid, and certain water-soluble organic copo]ymers. It has been found that the use of this combination of phosphonate and copolymer results in a synergistic effect in spite of the fact that th-e individual components are adversely affected when used in hard water.
According]y, the present invention provides a method of treating water, in particu]ar to reduce or prevent the deposition of so]id materia] in coo]ing water systems, which comprises incorporating in the water, _ 3 _ -2-phosphonobutane-1,2,4-tricarboxylic acid and a water soluble organic copolymer possessing carboxylic (including carboxylic anhydride) and sulphonate groups.
While it is possible to incorporate the phosphonate and copo]ymer separately it wi]l be appreciated that it will generally be more convenient to incorporate them together in the form of a composition. Accordingly, the present invention also provides a composition suitable for addition to water to reduce or prevent deposition of solid material therein, comprising the aforesaid phosphonate and copolymer, as defined below.
In general, the copolymers used in the present invention are viny~ addition type copolymers possessing recurring units of the formula:
~ CH
~1 1 /
Z X
and ¦ 12 \
Y I
~ - 4 wherein Rl represents hydrogen or lower a]kyl i.e. of 1 to 6 carbon atoms preferably ] to 4 carhon atoms, or -CH2COOH, R2 represents hydrogen or lower a]ky~, X
represents -COOH, Z represents hydrogen or -COOH or X and Z together represent -CO-O-CO-, and Y represents -SO3H, -C6HS SO3H (para) or -CONHO(R3)(R4) SO3H in Q P 2 or CH2 CH2 and R3 and R4, independently, represent hydrogen, pheny], substituted phenyl, C ]-12 linear or branched alkyl or C 3-12 cyc].oalkyl, especial]y methyl. Preferred such radicals include -CONH -C(CH3)(R~)-CH2-SO3H, especially where R3 represents methyl, and -CONHCH2SO3H.
The phosphonate and copolymers are generally used in the form of alkali metal, especia]ly sodium or potassium, ammonium, or lower amine salts although the use of the free acids, zinc or other salts of either or both is not excluded.
The molar proportion of the two types of recurring unit in the copolymer is generally from 5:95 to 95:5, more particularly from 25:75 to 75:25 and especi.ally about 5p:50. The copolymers generally possess a molecular weight from 500 to 750,000 and in particular from 1,000 to 10,000 and especially from 4,000 to 6,000. It will be appreciated that if the molecular weight of the copolymer is too high it tends to behave as a flocculating agent but this is not necessarily disadvantaqeous provided the flocculated material is sufficiently light to remain in suspension.
Preferred copo]ymers for use in the present invention include a copolymer of methacrylic acid and 2-acrylamido-2-methylpropane sulphonic acid (AMPS) in the form of, in 14~!8 particular, the sodium salt, especially in a molar ratio of about 1:1 and having a molecular weight of about 5,000, and a copolymer of styrene sulphonic acid and maleic acid in the form of, in particular, the sodium salt, especially in a molar ratio of about 3:1 and having a molecular weight of about 4,500.
The first units of the copolymers are generally de~ived from ethylenicalIy unsaturated acids such as maleic acid (or anhydride), acrylic acid and methacrylic acid. The second units of the copo]ymers are generally derived from ethy]enical]y unsaturated monomers; these monomers may either contain the sulphonate group or this group can be introduced by sulphonation of the copolymer.
The polymers used in the present invention can be obtained from the monomers using conventional polymerization processes. The styrene sulphonate polymers can be prepared by sulphonating a copolymer of styrene and maleic anhydride with a sulphur trioxide-organic phosphorus compound (see, for example, U. S. Patent
` llS~498 water precipitate or crystallize out or in some cases are deliberately caused to precipitate by the addition of, for example, phosphates and the resulting precipitate or sludge is conditioned so that it can readily be removed rather than adhere to the walls of the vessel.
The use of a variety of polycarboxylates and other low molecular weight polymers, including acrylate polymers, as dispersants in such water systems has been known for many years. It is well recognized, however, that these materials suffer a considerable decrease in effectiveness when used in hard water, for examp]e, water containing more than 300 ppm calcium hardness. This is obviously a serious deficiency in attempting to obtain higher concentration factors in coo]ing systems. The aim of the present invention is to provide a method which is more effective in preventing deposition in hard water than those current]y available.
According to the present invention it has surprisingly been found that this can be achieved hy the use of a specific combination of a specific phosphonate, viz., 2-phosphonobutane-1,2,4-tricarboxylic acid, and certain water-soluble organic copo]ymers. It has been found that the use of this combination of phosphonate and copolymer results in a synergistic effect in spite of the fact that th-e individual components are adversely affected when used in hard water.
According]y, the present invention provides a method of treating water, in particu]ar to reduce or prevent the deposition of so]id materia] in coo]ing water systems, which comprises incorporating in the water, _ 3 _ -2-phosphonobutane-1,2,4-tricarboxylic acid and a water soluble organic copolymer possessing carboxylic (including carboxylic anhydride) and sulphonate groups.
While it is possible to incorporate the phosphonate and copo]ymer separately it wi]l be appreciated that it will generally be more convenient to incorporate them together in the form of a composition. Accordingly, the present invention also provides a composition suitable for addition to water to reduce or prevent deposition of solid material therein, comprising the aforesaid phosphonate and copolymer, as defined below.
In general, the copolymers used in the present invention are viny~ addition type copolymers possessing recurring units of the formula:
~ CH
~1 1 /
Z X
and ¦ 12 \
Y I
~ - 4 wherein Rl represents hydrogen or lower a]kyl i.e. of 1 to 6 carbon atoms preferably ] to 4 carhon atoms, or -CH2COOH, R2 represents hydrogen or lower a]ky~, X
represents -COOH, Z represents hydrogen or -COOH or X and Z together represent -CO-O-CO-, and Y represents -SO3H, -C6HS SO3H (para) or -CONHO(R3)(R4) SO3H in Q P 2 or CH2 CH2 and R3 and R4, independently, represent hydrogen, pheny], substituted phenyl, C ]-12 linear or branched alkyl or C 3-12 cyc].oalkyl, especial]y methyl. Preferred such radicals include -CONH -C(CH3)(R~)-CH2-SO3H, especially where R3 represents methyl, and -CONHCH2SO3H.
The phosphonate and copolymers are generally used in the form of alkali metal, especia]ly sodium or potassium, ammonium, or lower amine salts although the use of the free acids, zinc or other salts of either or both is not excluded.
The molar proportion of the two types of recurring unit in the copolymer is generally from 5:95 to 95:5, more particularly from 25:75 to 75:25 and especi.ally about 5p:50. The copolymers generally possess a molecular weight from 500 to 750,000 and in particular from 1,000 to 10,000 and especially from 4,000 to 6,000. It will be appreciated that if the molecular weight of the copolymer is too high it tends to behave as a flocculating agent but this is not necessarily disadvantaqeous provided the flocculated material is sufficiently light to remain in suspension.
Preferred copo]ymers for use in the present invention include a copolymer of methacrylic acid and 2-acrylamido-2-methylpropane sulphonic acid (AMPS) in the form of, in 14~!8 particular, the sodium salt, especially in a molar ratio of about 1:1 and having a molecular weight of about 5,000, and a copolymer of styrene sulphonic acid and maleic acid in the form of, in particular, the sodium salt, especially in a molar ratio of about 3:1 and having a molecular weight of about 4,500.
The first units of the copolymers are generally de~ived from ethylenicalIy unsaturated acids such as maleic acid (or anhydride), acrylic acid and methacrylic acid. The second units of the copo]ymers are generally derived from ethy]enical]y unsaturated monomers; these monomers may either contain the sulphonate group or this group can be introduced by sulphonation of the copolymer.
The polymers used in the present invention can be obtained from the monomers using conventional polymerization processes. The styrene sulphonate polymers can be prepared by sulphonating a copolymer of styrene and maleic anhydride with a sulphur trioxide-organic phosphorus compound (see, for example, U. S. Patent
3 072 618).
In general the copolymer and phosphonate are used in the weight ratios from 10:1 to 1:10, more especia]ly from
In general the copolymer and phosphonate are used in the weight ratios from 10:1 to 1:10, more especia]ly from
4:1 to 1:4 and most especially about 1:1.
The dosage of phosphonate and copolymer depends, to some extent, on the nature of the aqueous system to be treated. Thus the phosphonate dosage depends to some extent on the calcium concentration while the copolymer dosage depends to some extent on the concentration of suspended solids. In genera~, however, it can be said that the concentration in the feed is from 0.01 to 500 ppm r ~ 6 ~5~498 of additive and, more particular]y, from 0.1 to 50 ppm. A
particularly preferred concentration is about 2.0 ppm.
However, the optimum concentration used must depend on the degree of build-up in the system.
It will be appreciatefl that other ingredients customari]y employed in water treatment such as alkali, lignin derivatives, biocides and corrosion inhibitors can also be employed.
The composition of the present invention will normally be in the form of an aqueous solution although other forms such as powders are not exc~uded.
The following Examples further illustrate the present invention. In these Examples two different types of tests were employed, namely a static test and a circulatory test. The details of these are as follows:
(i) In the static cylinder type test a suspension of graded particle size is allowed to stand for 24 hours in 250 ml measuring cylinders.
The height of the solid/liquid interface is noted -and the "% Hold Up" is calculated by dividing final height by origina~ height, expressed as a %.
(ii) A laboratory scale recircu]ating rig consisting of a centeifugal pump, a 5-liter vessel anfl a flow through cell for monitoring the optical transmission of a suspension unfler standard conflitions. The light transmission decreases with the better dispersion of the particu]ate matter in suspension.
-EXAMPLES ] to 9 These Examples show the effect of water containingvarying degrees of calcium hardness on a number of additives, using the static test.
Suspension of 1000 ppm China Clay. The results obtained are shown in Table 1.
TABLE I
Interface 2 Hold Up Example Additive Dose,ppm 100 ppm 300 ppm No. Ca2+water Ca2+ water 1 Blank ___ 0 0 2 Polymer 1 5 70 0 3 Polymer 2 5 71 0 4 Polymer 3 5 72 0 Polymer 4 5 69 0 6 Polymer 5 5 69 30 . Po3ymer 6 5 70 37.5 8 Po]ymer 7 5 68 15 9 Phospho-nate 1 5 60 0 __.___ .~ __.. .... ! . .. . __.. _ .. _ . ____ .~ 8 , . . .
polymer ] = Sodium po~yacrylate M Wt 2000 2 = Sodium polyacrylate M Wt 5000 3 = Sodium polymethacrylate M Wt 1000 4 = Sodium po]ymethacrylate M Wt 4500
The dosage of phosphonate and copolymer depends, to some extent, on the nature of the aqueous system to be treated. Thus the phosphonate dosage depends to some extent on the calcium concentration while the copolymer dosage depends to some extent on the concentration of suspended solids. In genera~, however, it can be said that the concentration in the feed is from 0.01 to 500 ppm r ~ 6 ~5~498 of additive and, more particular]y, from 0.1 to 50 ppm. A
particularly preferred concentration is about 2.0 ppm.
However, the optimum concentration used must depend on the degree of build-up in the system.
It will be appreciatefl that other ingredients customari]y employed in water treatment such as alkali, lignin derivatives, biocides and corrosion inhibitors can also be employed.
The composition of the present invention will normally be in the form of an aqueous solution although other forms such as powders are not exc~uded.
The following Examples further illustrate the present invention. In these Examples two different types of tests were employed, namely a static test and a circulatory test. The details of these are as follows:
(i) In the static cylinder type test a suspension of graded particle size is allowed to stand for 24 hours in 250 ml measuring cylinders.
The height of the solid/liquid interface is noted -and the "% Hold Up" is calculated by dividing final height by origina~ height, expressed as a %.
(ii) A laboratory scale recircu]ating rig consisting of a centeifugal pump, a 5-liter vessel anfl a flow through cell for monitoring the optical transmission of a suspension unfler standard conflitions. The light transmission decreases with the better dispersion of the particu]ate matter in suspension.
-EXAMPLES ] to 9 These Examples show the effect of water containingvarying degrees of calcium hardness on a number of additives, using the static test.
Suspension of 1000 ppm China Clay. The results obtained are shown in Table 1.
TABLE I
Interface 2 Hold Up Example Additive Dose,ppm 100 ppm 300 ppm No. Ca2+water Ca2+ water 1 Blank ___ 0 0 2 Polymer 1 5 70 0 3 Polymer 2 5 71 0 4 Polymer 3 5 72 0 Polymer 4 5 69 0 6 Polymer 5 5 69 30 . Po3ymer 6 5 70 37.5 8 Po]ymer 7 5 68 15 9 Phospho-nate 1 5 60 0 __.___ .~ __.. .... ! . .. . __.. _ .. _ . ____ .~ 8 , . . .
polymer ] = Sodium po~yacrylate M Wt 2000 2 = Sodium polyacrylate M Wt 5000 3 = Sodium polymethacrylate M Wt 1000 4 = Sodium po]ymethacrylate M Wt 4500
5 = Copolymer of methacry].ic acid/2 acrylamide 2 methyl propane sulphonic acid in 3:2 mole ratio
6 = Copolymer as in 5 but in a 1:1 mole ratio
7 = Sodium polystyrene sulphonate, M Wt 70 000 Phosphonate 1 = Nitrilotrismethylene phosphonic acid (as sodium salt) The above results show the serious effect of calcium hardness on the performance of some standard materials currently employed for dispersing particulate matter in cooling water systems. Although the copolymers 5, fi, and 7 give the best results, the deterioration in performance in hard water is still extremely undesirable. This test is severe hut does indicate relative strength and weaknesses on a comparative basis.
llS~498 EXAMPLES 10 to ]3 ~ he results in Table II were ohtained using the re-circulating rig after 5 hours using water containing 90 ppm China Clay Solids Suspension. They again indicate that the results in Table I are not due to the method of test.
TABLE II
. .
% Transmission in .
Example Additive Dose, 100 ppm 300 ppm No. ppm ca2+ ca2+
water water .. . . _ _ Blank --- 55 60 11 Polymer 6 5 33 36.4 12 Polymer 8 5 36.5 49.0 13 Phospho-- nate 2 5 34.0 48.0 Polymer 6 - Copolymer of methacrylic acid/2 acry]amide 2-methyl propane sulphonic acid 1:1 mole ratio Polymer 8 = Sodium polyacrylate M Wt 1000 Phosphonate 2 = 2-phosphonobutane -1,2,4-tricar-boxylic acid .~ 1.0 .~ .
~514~8 EXAMPI.~S 14 to 24 Table III ~ives the results of a number of tests run on the recirculating rig in order to ascertain the effect of adding a phosphonate to the polymer in question.
TABLE III
Recirculating rig - 90 ppm China Clay Solids Suspension Duration of test - 5 hours Dose level of additive ~ ppm in all cases, 300 ppm Ca2+
hardness water I .
~ Example No. Additive ~ Transmission _ . , 14 Blank 60 Polymer 6 36.3 lo Phosphonate 2 48.0 17 4/l ratio Polymer 6/Phosphonate 2 34.0 18 l/l ratio Polymer 6/Phosphonate 2 31.5 l9 1/4 ratio Polymer 6/Phosphonate 2 34.2 Phosphonate l 50.0 21 l/l ratio Polymer 6/Phosphonate 1 40.2 22 l/l ratio Polymer 8/Phosphonate 2 51.0 23 Polymer 9 40.8 _ l/l ratio Polymer 9/Phosphonate 2 38.4 Polymer 9 = Copolymer of Styrene sulphonate/Maleic acid in ratio 3:1 Molecular Wt. 4 500 .~, ., ~ , .
\ ~
115~4g8 These results show the synergistic effect of using the inve~tive phosphonate with the inventive polymers.
EXAMPLES 25 to 29 A static cylinder test was conducted using a 100 ppm suspension of China Clay in 300 ppm Ca2+ hardness water. The suspension in 250/ml measuring cylinders was allowed to settle for two hours, samples were then withdrawn at a given depth and the turbidity measured by a nephelometer. The efficiency of the additive as a dispersant was calculated from:
Final readinq of additive - Final reading of blank x 100 =
Initial reading of blank - Final reading of blank ~ efficiency ' , ,;
-. ' liS~
Test Additive Dose level, Efficiency _ ... _ ppm %
Polymer 6 5 33.1 Phosphonate 2 5 19.2 1:1 ratio Polymer 6/Phosphonate 2 5 42.6 26 Polymer 6 5 33.0 Phosphonate 3 5 25.0 1:1 ratio Polymer 6/Phosphonate 3 5 21.0 Phosphonate 1 5 16.6 1:1 ratio Polymer 6/Phosphonate 1 5 27.1 27 Polymer 6 5 29.2 Phosphonate 4 5 25.2 Phosphonate 5 5 10.4 1:1 ratio Polymer 6/Phosphonate 4 5 10.6 . 1:1 ratio Polymer 6/Phosphonate 5 5 20~8 28 Polymer 6 5 31.8 Phosphonate 6 5 17.3 1:1 ratio Polymer 6/Phosphonate 6 5 27.3 29 Polymer 6 5 32.7 Phosphonate 7 5 6.0 1:1 ratio Polymer 6/Phosphonate 7 5 17.7 liS149~3 Phosphonate 3 = Hexamethylene diamine tetramethylene . phosphonic acid. hosphonate 4 = N,N-bis(carboxymethyl)imino methylenephosphonic acid. hosphonate 5 = N,carboxymethyl imino di(methylene phosphonic acid~. hosphonate 6 = N,carboxymethyl imino monomethylene phosphonic acid. hosphonate 7 = Hydroxyethylidene diphosphonic acid.
It can be seen that only phosphonate 2, 2-phosphono- utane-1,2,4-tricarboxylic acid, gives a synergistic ffect.
.
.
'
llS~498 EXAMPLES 10 to ]3 ~ he results in Table II were ohtained using the re-circulating rig after 5 hours using water containing 90 ppm China Clay Solids Suspension. They again indicate that the results in Table I are not due to the method of test.
TABLE II
. .
% Transmission in .
Example Additive Dose, 100 ppm 300 ppm No. ppm ca2+ ca2+
water water .. . . _ _ Blank --- 55 60 11 Polymer 6 5 33 36.4 12 Polymer 8 5 36.5 49.0 13 Phospho-- nate 2 5 34.0 48.0 Polymer 6 - Copolymer of methacrylic acid/2 acry]amide 2-methyl propane sulphonic acid 1:1 mole ratio Polymer 8 = Sodium polyacrylate M Wt 1000 Phosphonate 2 = 2-phosphonobutane -1,2,4-tricar-boxylic acid .~ 1.0 .~ .
~514~8 EXAMPI.~S 14 to 24 Table III ~ives the results of a number of tests run on the recirculating rig in order to ascertain the effect of adding a phosphonate to the polymer in question.
TABLE III
Recirculating rig - 90 ppm China Clay Solids Suspension Duration of test - 5 hours Dose level of additive ~ ppm in all cases, 300 ppm Ca2+
hardness water I .
~ Example No. Additive ~ Transmission _ . , 14 Blank 60 Polymer 6 36.3 lo Phosphonate 2 48.0 17 4/l ratio Polymer 6/Phosphonate 2 34.0 18 l/l ratio Polymer 6/Phosphonate 2 31.5 l9 1/4 ratio Polymer 6/Phosphonate 2 34.2 Phosphonate l 50.0 21 l/l ratio Polymer 6/Phosphonate 1 40.2 22 l/l ratio Polymer 8/Phosphonate 2 51.0 23 Polymer 9 40.8 _ l/l ratio Polymer 9/Phosphonate 2 38.4 Polymer 9 = Copolymer of Styrene sulphonate/Maleic acid in ratio 3:1 Molecular Wt. 4 500 .~, ., ~ , .
\ ~
115~4g8 These results show the synergistic effect of using the inve~tive phosphonate with the inventive polymers.
EXAMPLES 25 to 29 A static cylinder test was conducted using a 100 ppm suspension of China Clay in 300 ppm Ca2+ hardness water. The suspension in 250/ml measuring cylinders was allowed to settle for two hours, samples were then withdrawn at a given depth and the turbidity measured by a nephelometer. The efficiency of the additive as a dispersant was calculated from:
Final readinq of additive - Final reading of blank x 100 =
Initial reading of blank - Final reading of blank ~ efficiency ' , ,;
-. ' liS~
Test Additive Dose level, Efficiency _ ... _ ppm %
Polymer 6 5 33.1 Phosphonate 2 5 19.2 1:1 ratio Polymer 6/Phosphonate 2 5 42.6 26 Polymer 6 5 33.0 Phosphonate 3 5 25.0 1:1 ratio Polymer 6/Phosphonate 3 5 21.0 Phosphonate 1 5 16.6 1:1 ratio Polymer 6/Phosphonate 1 5 27.1 27 Polymer 6 5 29.2 Phosphonate 4 5 25.2 Phosphonate 5 5 10.4 1:1 ratio Polymer 6/Phosphonate 4 5 10.6 . 1:1 ratio Polymer 6/Phosphonate 5 5 20~8 28 Polymer 6 5 31.8 Phosphonate 6 5 17.3 1:1 ratio Polymer 6/Phosphonate 6 5 27.3 29 Polymer 6 5 32.7 Phosphonate 7 5 6.0 1:1 ratio Polymer 6/Phosphonate 7 5 17.7 liS149~3 Phosphonate 3 = Hexamethylene diamine tetramethylene . phosphonic acid. hosphonate 4 = N,N-bis(carboxymethyl)imino methylenephosphonic acid. hosphonate 5 = N,carboxymethyl imino di(methylene phosphonic acid~. hosphonate 6 = N,carboxymethyl imino monomethylene phosphonic acid. hosphonate 7 = Hydroxyethylidene diphosphonic acid.
It can be seen that only phosphonate 2, 2-phosphono- utane-1,2,4-tricarboxylic acid, gives a synergistic ffect.
.
.
'
Claims (4)
1. Method of suspending sediment in cooling water systems that comprises adding thereto 2-phosphonobutane-1,2,4-tricarboxylic acid and a copolymer, in a total dosage of about 0.01-500 ppm; said copolymer consisting essentially of the repeating units:
and wherein R1 represents hydrogen or lower alkyl of 1 to 6 carbon atoms, or -CH2COOH, R2 represents hydrogen or lower alkyl, X represents -COOH, Z represents hydrogen or -COOH, or X and Z together represent -CO-O-CO-, and Y
represents -SO3H, -C6H5SO3H (para) or -CONHQ(R3)(R4) SO3H in which Q represents -CH2- or -CH2-CH2- and R3 and R4, independently, represent hydrogen, phenyl, substituted phenyl, C 1-12 linear or branched alkyl or C 3-12 cycloalkyl.
and wherein R1 represents hydrogen or lower alkyl of 1 to 6 carbon atoms, or -CH2COOH, R2 represents hydrogen or lower alkyl, X represents -COOH, Z represents hydrogen or -COOH, or X and Z together represent -CO-O-CO-, and Y
represents -SO3H, -C6H5SO3H (para) or -CONHQ(R3)(R4) SO3H in which Q represents -CH2- or -CH2-CH2- and R3 and R4, independently, represent hydrogen, phenyl, substituted phenyl, C 1-12 linear or branched alkyl or C 3-12 cycloalkyl.
2. Method according to Claim 1 in which the copolymer is a copolymer of methacrylic acid/2 acrylamido 2 methyl propane sulfonic acid.
3. Method according to Claim 1 in which the copolymer is a copolymer of styrene sulfonic acid and maleic acid.
4. Method according to any one of Claim 1, Claim 2, or Claim 3 in which the total dosage of phosphonate and copolymer is 0.1-50 ppm.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7936773 | 1979-10-23 | ||
| GB7936773 | 1979-10-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1151498A true CA1151498A (en) | 1983-08-09 |
Family
ID=10508725
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000362311A Expired CA1151498A (en) | 1979-10-23 | 1980-10-14 | Treatment of aqueous systems |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US4432879A (en) |
| CA (1) | CA1151498A (en) |
| DE (1) | DE3039356A1 (en) |
| ES (1) | ES8203802A1 (en) |
| FR (1) | FR2467824B1 (en) |
| IT (1) | IT1133966B (en) |
| MY (1) | MY8500514A (en) |
| SE (1) | SE441921B (en) |
Families Citing this family (40)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4588519A (en) * | 1982-01-29 | 1986-05-13 | Dearborn Chemical Company | Method of inhibiting corrosion of iron base metals |
| US4663053A (en) * | 1982-05-03 | 1987-05-05 | Betz Laboratories, Inc. | Method for inhibiting corrosion and deposition in aqueous systems |
| US4929362A (en) * | 1983-10-26 | 1990-05-29 | Betz Laboratories, Inc. | Calcium phosphate scale control methods |
| US4895664A (en) * | 1983-10-26 | 1990-01-23 | Betz Laboratories, Inc. | Water treatment polymers and methods of use thereof |
| US4869845A (en) * | 1983-10-26 | 1989-09-26 | Betz Laboratories, Inc. | Water treatment compositions |
| US4849129A (en) * | 1988-05-06 | 1989-07-18 | Betz Laboratories, Inc. | Water treatment polymers and methods of use thereof |
| US4863614A (en) * | 1983-10-26 | 1989-09-05 | Betz Laboratories, Inc. | Water treatment polymers and methods of use thereof |
| US4906383A (en) * | 1983-10-26 | 1990-03-06 | Betz Laboratories, Inc. | Novel amine-containing copolymers and their use |
| US4980433A (en) * | 1983-10-26 | 1990-12-25 | Betz Laboratories, Inc. | Novel amine-containing copolymers and their use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL250070A (en) * | 1959-04-01 | |||
| DE1806594C3 (en) * | 1968-11-02 | 1979-05-03 | Joh. A. Benckiser Gmbh, 6700 Ludwigshafen | Use of a mixture of aminoalkylenephosphonic acid and polymeric compounds to prevent stone-forming deposits in aqueous systems |
| DE2061838C3 (en) * | 1970-12-16 | 1980-06-12 | Bayer Ag, 5090 Leverkusen | 2-phosphono-butane-1,2-dicarboxylic acid derivatives, processes for their preparation and compositions containing these compounds |
| US3886204A (en) * | 1970-12-16 | 1975-05-27 | Bayer Ag | 2-Phosphono-butane-1,2,3,4-tetracarboxylic acids |
| US3709816A (en) * | 1971-07-01 | 1973-01-09 | Calgon Corp | Control of alluvial and other deposits in aqueous systems |
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| US3890228A (en) * | 1973-04-13 | 1975-06-17 | Chemed Corp | Polyacrylate-polyphosphonic acid treatment in aqueous systems |
| DE2325829C2 (en) * | 1973-05-22 | 1982-04-01 | Henkel KGaA, 4000 Düsseldorf | Sequestrants |
| US3992318A (en) * | 1973-10-09 | 1976-11-16 | Drew Chemical Corporation | Corrosion inhibitor |
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| CA1062983A (en) * | 1975-09-08 | 1979-09-25 | Joseph J. Schuck | Copolymers for the control of the formation and deposition of materials in aqueous mediums |
| DE2643422A1 (en) * | 1976-09-21 | 1978-03-30 | Kurita Water Ind Ltd | WATER TREATMENT PRODUCTS AND METHODS FOR TREATMENT OF WATER |
| US4118318A (en) * | 1976-10-26 | 1978-10-03 | Calgon Corporation | Gas scrubber scale and deposit control |
| GB1539974A (en) * | 1976-11-10 | 1979-02-07 | Ciba Geigy Ag | Method of inhibiting corrosion and scaling of metals in contact with water |
| US4048066A (en) * | 1976-11-17 | 1977-09-13 | Chemed Corporation | Method of inhibiting scale |
| DE2723834A1 (en) * | 1977-05-26 | 1978-12-07 | Bayer Ag | REPRODUCTION PRODUCTS OF PHOSPHONOCARBONIC ACIDS WITH ALCOHOLS |
| CA1114978A (en) * | 1978-06-15 | 1981-12-22 | Chih M. Hwa | Sludge conditioning composition for scale inhibition in water |
| US4255259A (en) * | 1979-09-18 | 1981-03-10 | Chemed Corporation | Scale inhibition |
-
1980
- 1980-10-14 CA CA000362311A patent/CA1151498A/en not_active Expired
- 1980-10-18 DE DE19803039356 patent/DE3039356A1/en active Granted
- 1980-10-20 SE SE8007353A patent/SE441921B/en not_active IP Right Cessation
- 1980-10-21 IT IT25479/80A patent/IT1133966B/en active
- 1980-10-22 ES ES496150A patent/ES8203802A1/en not_active Expired
- 1980-10-22 FR FR8022615A patent/FR2467824B1/en not_active Expired
-
1981
- 1981-08-28 US US06/297,525 patent/US4432879A/en not_active Expired - Lifetime
-
1985
- 1985-12-30 MY MY514/85A patent/MY8500514A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| FR2467824A1 (en) | 1981-04-30 |
| SE441921B (en) | 1985-11-18 |
| DE3039356C2 (en) | 1989-03-30 |
| US4432879A (en) | 1984-02-21 |
| DE3039356A1 (en) | 1981-05-14 |
| ES496150A0 (en) | 1982-04-01 |
| ES8203802A1 (en) | 1982-04-01 |
| SE8007353L (en) | 1981-04-24 |
| IT8025479A0 (en) | 1980-10-21 |
| IT1133966B (en) | 1986-07-24 |
| FR2467824B1 (en) | 1985-12-20 |
| MY8500514A (en) | 1985-12-31 |
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