CA2003915A1 - Descaling composition and methods for use - Google Patents
Descaling composition and methods for useInfo
- Publication number
- CA2003915A1 CA2003915A1 CA 2003915 CA2003915A CA2003915A1 CA 2003915 A1 CA2003915 A1 CA 2003915A1 CA 2003915 CA2003915 CA 2003915 CA 2003915 A CA2003915 A CA 2003915A CA 2003915 A1 CA2003915 A1 CA 2003915A1
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- Prior art keywords
- water
- composition
- scale
- group
- heat
- 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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Abstract
ABSTRACT
A composition comprises: (a) a hydroxycarboxylic acid having the formula ; (b) an alkanolamine having the formula
A composition comprises: (a) a hydroxycarboxylic acid having the formula ; (b) an alkanolamine having the formula
Description
Z00391~i ~' `~ Dl~SCALING COMPOSITION AND METHODS OF USE
This application is a continuation-in-part of my co-pending i U.S.A. application, Serial Number 195,851, filed May 19, 1988 ' This invention relates to chemical compositions and methods of use thereof which are useful in removing and preventing reformation of water scale on various surfaces.
' ,:
In an even more particular respect, the invention relates to ~- 10 such compositions which are especially adapted for use in heat-~` exchange systems utiliæing water as a recirculating heat-exchange !, ' .I medium.
"Scale" is a general term which describes precipitates from aqueous fluids which deposit on surfaces in contact with water, ~15 generally as a result of exceeding the limit of solubility of such materials in the water, e.g., by evaporation of the water or by - ~ otherwise concentrating these components. Such scale materials . ~ include compounds such as sulfates, oxides, carbonates, halides and the like. Examples include calcium carbonate and iron oxides.
To be effective, a descaling composition should break down components of scale. Primarily, the descaling composition should remove carbonates and sulfates.
A number of methods have been devised to prevent or remove scale. Foriexample,~Rubin, in U.S. Patent No. 3,075,924 teaches ~25 a detergent composition which includes a long chain aliphatic sulfate and an alkylamine acetic acid.
'f',~
~: ~
~ .~ . , 200391~:i , ~, Clark et al, in U.S. Patent No. 3,053,897, disclosed compositions for the removal of rust and scale. Clark teaches the ~,use of triethanolamine in combination with an alXali and an aliphatic hydroxy acid. Clark also teaches the use o~ alkali metal salts of sulfonated fatty acids.
Conklin et al, in U.S. Patent No. 2,847,384, disclosed a descaling composition which includes a non-ionlc wetting agent which is a mixture of polyoxythylene-propylene polymeric compounds with sodium xylyene sulfate.
Petroy, U.S. Patent No. 3,699,047, employed zinc ion in a scale inhibiting composition which may also include an alkyleneamine-acetic acid compound.
Monson, in U.S. Patent No. 2,589,195, disclosed an inhibiting scale composition which includes a triethanolamine which is reacted with an ethylene oxide to form an amine having a number of ethylene oxide units. The terminal hydroxy groups are acylated with a fatty ~: acid.
l ~ Further examples of prior art descaling compositions are . "~disclosed in the Abadi patents, U.S. 4,435,303 and 4,595,517.
~; ~As yet, however, such prior art does not provide economically effective methods for preventing scale formation, particularly in large industrial applications where recirculating water containing scale-forming components is used as a circulating medium in heat-~- ~exchange equipment, e.g., boilers, coolers, etc. Instead, the `".'.t,'' ~common approach in the ! prior àrt is to employ expensive and complicated deionizing and other water purification pretreatment processes to reduce the initial level of scale-forming components .~ -~in the aqueous heat-exchange medium. Also it is common practice ¦to bleod sizabl- guantitios o~ th- aquoous hcat--xohange m-dium from the system to avoid build up of concentrations o~ the scale-forming components which exceed their solubility limits in the cooling or heating water. The water removed to control the concentration of scale-forming components in such heat-exchange systems is called "blowdown".
It would be highly desirable to reduce the amount o~ blowdown encountered in operating conventional heat-exchange systems, particularly evaporative cooling systems which utilize water as the heat-exchange medium, as the problem is disposing o~ the blowdown has become increasingly serious and the cost of the makeup water constitutes a significant cost element in the operation of such systems.
Additionally, it would be desirable to provide improved ', descaling compositions for use in a wide variety of end-use,~ 15 applications in which water conservation or waste disposal is a significant factor. For example, it would be highly desirable to achieve such results in the operation of direct heat-exchange systems such as automotive radiators, and the like. Also, reducing ~; the solubility of scale-forming components in water is important in residential use, e.g., tub and tile cleaners and the like, and ;~ the metal scavenging effect of such compositions would provide desirable results in widely diverse products such as plant roods, medicines, etc.
Therefore, the principal object of the present invention is to provide an improved composition for solubilizing scale and scale-forming components in aqueous systems. -~ :;'`. .
Another object of the invention is to provide methods for operating heat-exchange systems which reduce the amount of blowdown -~ `
required to prevent scale formation.
},~
:
200~915 Still other objects of the invention are to provide compositions for solubilizing scale-forming components in aqueous systems and utilizing such capabilities to improve the qualities of various household, industrial and medical products.
Briefly, in accordance with the invention, a composition is provided which consists essentially of a hydroxycarboylic acid, an amine and a monocyclic aryl surfactant.
According to another embodiment of the invention, methods for removing water scale from surfaces are provided which include the step of contacting the surfaces with water containing a minor effective amount of this composition.
According to a more specific embodiment of the invention, a method is provided for operating a heat-exchange system which utilizes water as a heat-exchange medium. These methods include the step of circulating in the system a water heat-exchange medium containing scale-forming components and an effective amount of this composition, i.e., in an amount sufficient to maintain the scale-forming components in solution.
- The composition of the present invention is in the form of a ~20 concentrate which can be further diluted as required by the particular end-use of the composition.
The hydroxycarboxylic acids used in the practice of the invention have the structural formula 1 ~ ! O
~-~ HO-(C-Rl)-C-OH
wherein Rl is hydrogen, a branched or straight chain alkyl, cycloalkyl, or aryl substituent having one or more carbon atoms and .
:~
Z0039~
.
; forms a stable C-Rl group which does not inactivate the carboxylic acid group. The preferred hydroxycarboxylic acid is hydroxyacetic acid wherein C-Rl is a methane radical.
The alkonolamines used in the practice of the lnventlon have the structural formula R
'1 12 ,, ~O-C-R6-N-R5 i~ wherein R6 is a branched or straight chain alkyl group having ~rom 0-5 carbon atoms, and R2, R3, R4 and R5 are selected from the group consisting of hydrogen, a branched or straight chain alkyl group, a cycloalkyl group or aryl group, such that the cumulative electro-chemical effect of the substituent groups does not create an overly '~ positive charge and negate the basicity of the alXanolamine.
This application is a continuation-in-part of my co-pending i U.S.A. application, Serial Number 195,851, filed May 19, 1988 ' This invention relates to chemical compositions and methods of use thereof which are useful in removing and preventing reformation of water scale on various surfaces.
' ,:
In an even more particular respect, the invention relates to ~- 10 such compositions which are especially adapted for use in heat-~` exchange systems utiliæing water as a recirculating heat-exchange !, ' .I medium.
"Scale" is a general term which describes precipitates from aqueous fluids which deposit on surfaces in contact with water, ~15 generally as a result of exceeding the limit of solubility of such materials in the water, e.g., by evaporation of the water or by - ~ otherwise concentrating these components. Such scale materials . ~ include compounds such as sulfates, oxides, carbonates, halides and the like. Examples include calcium carbonate and iron oxides.
To be effective, a descaling composition should break down components of scale. Primarily, the descaling composition should remove carbonates and sulfates.
A number of methods have been devised to prevent or remove scale. Foriexample,~Rubin, in U.S. Patent No. 3,075,924 teaches ~25 a detergent composition which includes a long chain aliphatic sulfate and an alkylamine acetic acid.
'f',~
~: ~
~ .~ . , 200391~:i , ~, Clark et al, in U.S. Patent No. 3,053,897, disclosed compositions for the removal of rust and scale. Clark teaches the ~,use of triethanolamine in combination with an alXali and an aliphatic hydroxy acid. Clark also teaches the use o~ alkali metal salts of sulfonated fatty acids.
Conklin et al, in U.S. Patent No. 2,847,384, disclosed a descaling composition which includes a non-ionlc wetting agent which is a mixture of polyoxythylene-propylene polymeric compounds with sodium xylyene sulfate.
Petroy, U.S. Patent No. 3,699,047, employed zinc ion in a scale inhibiting composition which may also include an alkyleneamine-acetic acid compound.
Monson, in U.S. Patent No. 2,589,195, disclosed an inhibiting scale composition which includes a triethanolamine which is reacted with an ethylene oxide to form an amine having a number of ethylene oxide units. The terminal hydroxy groups are acylated with a fatty ~: acid.
l ~ Further examples of prior art descaling compositions are . "~disclosed in the Abadi patents, U.S. 4,435,303 and 4,595,517.
~; ~As yet, however, such prior art does not provide economically effective methods for preventing scale formation, particularly in large industrial applications where recirculating water containing scale-forming components is used as a circulating medium in heat-~- ~exchange equipment, e.g., boilers, coolers, etc. Instead, the `".'.t,'' ~common approach in the ! prior àrt is to employ expensive and complicated deionizing and other water purification pretreatment processes to reduce the initial level of scale-forming components .~ -~in the aqueous heat-exchange medium. Also it is common practice ¦to bleod sizabl- guantitios o~ th- aquoous hcat--xohange m-dium from the system to avoid build up of concentrations o~ the scale-forming components which exceed their solubility limits in the cooling or heating water. The water removed to control the concentration of scale-forming components in such heat-exchange systems is called "blowdown".
It would be highly desirable to reduce the amount o~ blowdown encountered in operating conventional heat-exchange systems, particularly evaporative cooling systems which utilize water as the heat-exchange medium, as the problem is disposing o~ the blowdown has become increasingly serious and the cost of the makeup water constitutes a significant cost element in the operation of such systems.
Additionally, it would be desirable to provide improved ', descaling compositions for use in a wide variety of end-use,~ 15 applications in which water conservation or waste disposal is a significant factor. For example, it would be highly desirable to achieve such results in the operation of direct heat-exchange systems such as automotive radiators, and the like. Also, reducing ~; the solubility of scale-forming components in water is important in residential use, e.g., tub and tile cleaners and the like, and ;~ the metal scavenging effect of such compositions would provide desirable results in widely diverse products such as plant roods, medicines, etc.
Therefore, the principal object of the present invention is to provide an improved composition for solubilizing scale and scale-forming components in aqueous systems. -~ :;'`. .
Another object of the invention is to provide methods for operating heat-exchange systems which reduce the amount of blowdown -~ `
required to prevent scale formation.
},~
:
200~915 Still other objects of the invention are to provide compositions for solubilizing scale-forming components in aqueous systems and utilizing such capabilities to improve the qualities of various household, industrial and medical products.
Briefly, in accordance with the invention, a composition is provided which consists essentially of a hydroxycarboylic acid, an amine and a monocyclic aryl surfactant.
According to another embodiment of the invention, methods for removing water scale from surfaces are provided which include the step of contacting the surfaces with water containing a minor effective amount of this composition.
According to a more specific embodiment of the invention, a method is provided for operating a heat-exchange system which utilizes water as a heat-exchange medium. These methods include the step of circulating in the system a water heat-exchange medium containing scale-forming components and an effective amount of this composition, i.e., in an amount sufficient to maintain the scale-forming components in solution.
- The composition of the present invention is in the form of a ~20 concentrate which can be further diluted as required by the particular end-use of the composition.
The hydroxycarboxylic acids used in the practice of the invention have the structural formula 1 ~ ! O
~-~ HO-(C-Rl)-C-OH
wherein Rl is hydrogen, a branched or straight chain alkyl, cycloalkyl, or aryl substituent having one or more carbon atoms and .
:~
Z0039~
.
; forms a stable C-Rl group which does not inactivate the carboxylic acid group. The preferred hydroxycarboxylic acid is hydroxyacetic acid wherein C-Rl is a methane radical.
The alkonolamines used in the practice of the lnventlon have the structural formula R
'1 12 ,, ~O-C-R6-N-R5 i~ wherein R6 is a branched or straight chain alkyl group having ~rom 0-5 carbon atoms, and R2, R3, R4 and R5 are selected from the group consisting of hydrogen, a branched or straight chain alkyl group, a cycloalkyl group or aryl group, such that the cumulative electro-chemical effect of the substituent groups does not create an overly '~ positive charge and negate the basicity of the alXanolamine.
2`~ 15 Preferred alkanolamines of this general formula consist of methanolamine and triethanolamine.
The alkalimetal monocyclic aryl sulfonates use in the concentrate composition include sodium and potassium salts of the sulfurio acids of tolerance and xylene, e.g. 2,3-dimethyl ~2-0 benzenesulfonate: 2,4-dimethylbenzenesulfonate; 2,5-; dimethylbenzesulfonate; 3,4-dimethylbenzesulfonate, 4-ethylbenzemesulfonte and the like. Sodium dimethyl benzene sulfonates and mixtures thereof are preferred.
The compositions of the invention can be prepared by ~25 dissolving the alkanolamine in a suitable solvent, suitably an aqueous alcoholic solvent, and then mixing the amine solution with the surfactant. The mixing steps are preferably carried out under high shear conditions until complete solution and reaction occurs.
"~
` : ~S~ ~`
,.
,,.;
Suitable alcohol solvents include those having the structural formula wherein Rl, R2, R3 are each selected from the group de~ined above for Rl R5. Preferred alcohols of this general formula are methanol, ethanol, propanol and ethylene glycol.
In my previous co-pending U.S.A. application S/N 195,851, I
described compositions in which the amine-sulfonate composition further reacted with. However, I have now determined that such further steps can be omitted. one may to obtain a useful, desirable product if the carboxylic acid is added directly to the composition. -I have further determined that alcohol used to dissolve the -~ amine is largely dissipated during the exothermic mixing with the sulfonate. Substantial alcohol remaining in the concentrate composition does not materially increase the effectiveness of the product.
The volume percentage of the hydrocarboxylic acid to the total ;~ mixture is in the range of about 25-60%, preferably about 35-45~.
The efficacious ratio of hydrocarboxylic acid to alhauolamine is in the range of 0.7 - 10, preferably about 2.0 - 3.5. -~
In use,~the agueous chemical composition of the present ~25 invention is added to water in a recirculating agueous system.
Agueous systems which are non-recirculating may be recirculated to increase ths rate of reaction. If a relatively higher reaction ; rate is not reguired, non-recirculating systems may remain 80.
Z0039~
Solutions of about 0.5% to 5%, preferably ~rom 0.5% to 1.0% by volume, of the present invention to water are usually suf~icient to maintain a previously cleaned aqueous system. To clean a scaled and/or rusted aqueous system, solutions o~ up to 50%, by volume, of the aqueous chemical composition in water may be employed.
Higher concentrations and higher reaction temperatures increase the rate of the descaling and antioxidizing reaction. It has been found, however, that concentrations in excess of 50% by volume do 10 not exhibit statistically significant further increases in reaction rate.
To further illustrate the preferred practice of the invention, the following examples are presented.
,~
,~
, ~ .
: ~
~ .
.
, ~ .
:
:
,.
~:~
',~;
,~ ~ :
. ~ .
200391 ~
A dilute ethanol-water solvent is prepared by agitating a mixture of water and ethanol (0.015% by volume~. To this ethanolic aqueous solvent is added an equal volume o~ triethanolamine and the resultant mixture is agitatad for an additional 30 minutes at room temperature and pressure, resulting in complete solution of the amine. To this amine solution is added about 30% by volume of sodium xylene sulfonate and shear agitation is continued for an additional approximately 30 minutes. The reaction begins at room temperature but the temperature of the reaction mixture rises to ~ m approximately lOO-F during this mixing period. To this mixture is added about 40~ by colume of hydroxyacetic acid and mixing is continued for an additional 10 minutes.
' ,' :
,~
,,,~
, , ~ Z003915 For use in residential evaporative cooler, egual parts o~ the concentrate of Example 1 and water are mixed in the evaporative cooler sump.
~ 9- ~,~
200:~9~5 For use in an industrial cooling tower, ~rom about 0.5 to 1.0%
by volume of the composition of Example 1 is added to the recirculating water in the system.
,~
:, .
-' , ' ' , ,.
~ ' .. : ,: .
~ .~-' :"'.' ' ~ ~ 1 0 ~ , . :
:
'~ -20039~5 A suitable residential tub and tile cleaning solution is prepared by physically admixing the following components in the indicated percentages by volume.
COMPONENTS PERCENTAGE
Water 56 Concentrate 33 Butylcellosolve .05 Monoethanolamine 10.95 Cherry scent trace ~ ,~
I,;
:~ ;
., ~
.
-11- .
",, ~
.~.~ - . . .
Z0039~S
EXAMPLE S
A suitable buffered descaling composition is prepared by physically admixing the following component~ in the indicated percentages by volume.
COMPONENTS PERCENTAGE
Hydrochloric acid 70 Product of Example 430 Cherry scent trace ~ ~ , ....
., - . ~
,~, :; :, ,::
`''~
`'~
~: : -,`~
,~
~`~4 ~-A suitable buffered descaling composition is prepared byphysically admixing the following components in the indicated percentages by volume.
COMPONENTS PERCENTAGE
Sulfuric acid 70 Product of Example 1 30 ,:
I ~
I :- ~ .
~ ~ , .~
~ 13-
The alkalimetal monocyclic aryl sulfonates use in the concentrate composition include sodium and potassium salts of the sulfurio acids of tolerance and xylene, e.g. 2,3-dimethyl ~2-0 benzenesulfonate: 2,4-dimethylbenzenesulfonate; 2,5-; dimethylbenzesulfonate; 3,4-dimethylbenzesulfonate, 4-ethylbenzemesulfonte and the like. Sodium dimethyl benzene sulfonates and mixtures thereof are preferred.
The compositions of the invention can be prepared by ~25 dissolving the alkanolamine in a suitable solvent, suitably an aqueous alcoholic solvent, and then mixing the amine solution with the surfactant. The mixing steps are preferably carried out under high shear conditions until complete solution and reaction occurs.
"~
` : ~S~ ~`
,.
,,.;
Suitable alcohol solvents include those having the structural formula wherein Rl, R2, R3 are each selected from the group de~ined above for Rl R5. Preferred alcohols of this general formula are methanol, ethanol, propanol and ethylene glycol.
In my previous co-pending U.S.A. application S/N 195,851, I
described compositions in which the amine-sulfonate composition further reacted with. However, I have now determined that such further steps can be omitted. one may to obtain a useful, desirable product if the carboxylic acid is added directly to the composition. -I have further determined that alcohol used to dissolve the -~ amine is largely dissipated during the exothermic mixing with the sulfonate. Substantial alcohol remaining in the concentrate composition does not materially increase the effectiveness of the product.
The volume percentage of the hydrocarboxylic acid to the total ;~ mixture is in the range of about 25-60%, preferably about 35-45~.
The efficacious ratio of hydrocarboxylic acid to alhauolamine is in the range of 0.7 - 10, preferably about 2.0 - 3.5. -~
In use,~the agueous chemical composition of the present ~25 invention is added to water in a recirculating agueous system.
Agueous systems which are non-recirculating may be recirculated to increase ths rate of reaction. If a relatively higher reaction ; rate is not reguired, non-recirculating systems may remain 80.
Z0039~
Solutions of about 0.5% to 5%, preferably ~rom 0.5% to 1.0% by volume, of the present invention to water are usually suf~icient to maintain a previously cleaned aqueous system. To clean a scaled and/or rusted aqueous system, solutions o~ up to 50%, by volume, of the aqueous chemical composition in water may be employed.
Higher concentrations and higher reaction temperatures increase the rate of the descaling and antioxidizing reaction. It has been found, however, that concentrations in excess of 50% by volume do 10 not exhibit statistically significant further increases in reaction rate.
To further illustrate the preferred practice of the invention, the following examples are presented.
,~
,~
, ~ .
: ~
~ .
.
, ~ .
:
:
,.
~:~
',~;
,~ ~ :
. ~ .
200391 ~
A dilute ethanol-water solvent is prepared by agitating a mixture of water and ethanol (0.015% by volume~. To this ethanolic aqueous solvent is added an equal volume o~ triethanolamine and the resultant mixture is agitatad for an additional 30 minutes at room temperature and pressure, resulting in complete solution of the amine. To this amine solution is added about 30% by volume of sodium xylene sulfonate and shear agitation is continued for an additional approximately 30 minutes. The reaction begins at room temperature but the temperature of the reaction mixture rises to ~ m approximately lOO-F during this mixing period. To this mixture is added about 40~ by colume of hydroxyacetic acid and mixing is continued for an additional 10 minutes.
' ,' :
,~
,,,~
, , ~ Z003915 For use in residential evaporative cooler, egual parts o~ the concentrate of Example 1 and water are mixed in the evaporative cooler sump.
~ 9- ~,~
200:~9~5 For use in an industrial cooling tower, ~rom about 0.5 to 1.0%
by volume of the composition of Example 1 is added to the recirculating water in the system.
,~
:, .
-' , ' ' , ,.
~ ' .. : ,: .
~ .~-' :"'.' ' ~ ~ 1 0 ~ , . :
:
'~ -20039~5 A suitable residential tub and tile cleaning solution is prepared by physically admixing the following components in the indicated percentages by volume.
COMPONENTS PERCENTAGE
Water 56 Concentrate 33 Butylcellosolve .05 Monoethanolamine 10.95 Cherry scent trace ~ ,~
I,;
:~ ;
., ~
.
-11- .
",, ~
.~.~ - . . .
Z0039~S
EXAMPLE S
A suitable buffered descaling composition is prepared by physically admixing the following component~ in the indicated percentages by volume.
COMPONENTS PERCENTAGE
Hydrochloric acid 70 Product of Example 430 Cherry scent trace ~ ~ , ....
., - . ~
,~, :; :, ,::
`''~
`'~
~: : -,`~
,~
~`~4 ~-A suitable buffered descaling composition is prepared byphysically admixing the following components in the indicated percentages by volume.
COMPONENTS PERCENTAGE
Sulfuric acid 70 Product of Example 1 30 ,:
I ~
I :- ~ .
~ ~ , .~
~ 13-
Claims (4)
1. A composition comprising:
(a) a hydroxycarboxylic acid having the formula ;
(b) an alkanolamine having the formula ;
and (c) an alkali metal monocyclic aryl sulfonate;
wherein R1-R5 are substituents selected from the group consisting of hydrogen straight chain alkyl, cycloalkyl or aryl groups, R6 is a branched or straight chain alkyl group having 0-5 carbon atoms, and R1 is such a substituent which does not inactivate the carboxylic acid group.
(a) a hydroxycarboxylic acid having the formula ;
(b) an alkanolamine having the formula ;
and (c) an alkali metal monocyclic aryl sulfonate;
wherein R1-R5 are substituents selected from the group consisting of hydrogen straight chain alkyl, cycloalkyl or aryl groups, R6 is a branched or straight chain alkyl group having 0-5 carbon atoms, and R1 is such a substituent which does not inactivate the carboxylic acid group.
2. A method for removing water scale from a surface, comprising contacting said surface with water containing an effective amount of the concentrate composition of Claim 1.
3. A method for reducing the rate of deposition of water scale upon a surface in contact with water containing scale forming components, said method comprising incorporating into said water from about 0.15 to about 1.0 percent by volume of the concentrate composition of Claim 1.
4. The method of operating a heat-exchange system using water as the heat-exchange medium, comprising circulating in said system water containing scale-forming components and an amount of the composition of Claim 1 effective to maintain said components in solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2003915 CA2003915A1 (en) | 1989-11-27 | 1989-11-27 | Descaling composition and methods for use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA 2003915 CA2003915A1 (en) | 1989-11-27 | 1989-11-27 | Descaling composition and methods for use |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2003915A1 true CA2003915A1 (en) | 1991-05-27 |
Family
ID=4143644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2003915 Abandoned CA2003915A1 (en) | 1989-11-27 | 1989-11-27 | Descaling composition and methods for use |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2003915A1 (en) |
-
1989
- 1989-11-27 CA CA 2003915 patent/CA2003915A1/en not_active Abandoned
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