CA1299965C - Use of sulfamic acid to inhibit phosphonate decomposition by chlorine-bromine mixtures - Google Patents
Use of sulfamic acid to inhibit phosphonate decomposition by chlorine-bromine mixturesInfo
- Publication number
- CA1299965C CA1299965C CA000579721A CA579721A CA1299965C CA 1299965 C CA1299965 C CA 1299965C CA 000579721 A CA000579721 A CA 000579721A CA 579721 A CA579721 A CA 579721A CA 1299965 C CA1299965 C CA 1299965C
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- Canada
- Prior art keywords
- chlorine
- bromide
- decomposition
- sulfamic acid
- phosphonate
- 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.)
- Expired - Fee Related
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
- C02F1/766—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens by means of halogens other than chlorine or of halogenated compounds containing halogen other than chlorine
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Detergent Compositions (AREA)
Abstract
Abstract The decomposition of phosphonates by chlorine-bromine solutions present in industrial process waters can be diminished or prevented by treating such waters with sulfamic acid.
Description
12~9~6S
Introduction The use of phosphonates for scale and corrosLon control in recirculating cooling water is widely practiced as is the use of chlorine for microbiological control. However, the use of these two practices simultaneously can cause problems. Chlorine has been demonstrated to break down many phosphonates to a significant extent. When this happens in a field application, the effectiveness of the phosphonate as a scale control agent is degraded and the orthophosphate which is a product of this reaction can contribute to scaling problems. Even some reputedly chlorine-resistant phosphonates such as l,l-hydroxyethylidine diphosphonic acid (HEDP) are not sufficiently stable for some industrial applications where continuous chlorination is practiced. Under carefully controlled conditions where the free chlorine residual is kept at a low constant level, breakdown of HEDP is minimal. However, under the less well controlled ¦
environment found in a typical plant cooling circuit, excessive chlorine levels are frequently observed. Under these conditions, HEDP or other phosphonates can break down to a sufficient degree to cause problems. Additionally, a number of dissolved ions typically found in cooling waters have been found to catalyze the breakdown of phosphonates.
The problem described above has been overcome by treating such cooling waters with sulfamic acid or other compounds ~his technoLogy is disclosed in U.S. 4,642,194-ll ~ I
. ~ '' - 2 - ~
~ - 12~9965 It has been observed that when the bioclde in cooling waters is a mixture of chlorine in combination with a bromide salt capable of releasing bromide ions, a much more profound and exaggerated degradation of the phosphonates occurs. It is an object of the invention to prevent this unexpected, rapid decomposition of phosphonates by mixtures of chlorine and bromide ions present as biocides in industrial cooling waters.
The Invention The invention is a method for preventing the decomposition of phosphonates which are present in cooling waters to prevent scale and corrosion in industrial cooling waters which also contain as a biocide the combination of chlorine and a bromide salt which releases bromide ions which comprises treating said waters with at least 1 ppm of sulfamic acid for each ppm of bromide.
The Chlorine-Bromide Biocides The biocides comprise a chlorine solution and a bromide salt capable of releasing bromide ions to the chlorine solution.
Suitable bromide salts include the alkali and alkaline earth metal bromides but are not limited thereto. For instance, magnesium bromide, calcium bromide, sodium bromide, potassium bromide, ammonium bromide, and the like salts can be used, either singly or as mixture of two or more as desired.
A bromide salt, for example, sodium bromide, when introduced into a chlorine solution in which the chlorine is present mostly as hypochlorous acid, has been shown to at least partially displace chlorine, resulting in the formation of the .
active biocide, hypobromous acid, and innoxious sodium chloride by-product as follows: ¦
NaBr~HOCl--NaCl+HOBr In present chlorination installations, the bromide salt can merely be introduced downstream of the chlorine educting water line, at which point gaseous chlorine has already been introduced into a water stream and hydrolyzed to form the hypochlorous acid and hydrochloric acid, which usually would be an acidic chlorine solution. It can also be introduced into chlorine solutions formed from sodium or calcium hypochlorite or other chlorine donors and will undergo the same reactions.
The bromide salts are themselves generally innoxious salts and thus their use in combination with chlorine presents no new or unknown hazards. Advantages of using the bromide salts along with chlorine is the formation of a more effective biocide solution due to the formation of hypobromous acid. The use of bromide salts along with chlorine for improved biocontrol effectiveness is described in detail in the following patents:
U.S. 4,451,376 and U.S. 4,643,835.
The degree of conversion of hypochlorous acid to hypobromous acid depends of course to an extent on the relative proportion of bromide salt to hypochlorous acid which are combined to form the composition and other factors affecting the displacement of chlorine with bromine.
Although the present invention encompasses any proportion of bromide salt to chlorine, in a preferred embodiment the present invention includes the combination of bromide salt to chlorine as hypochlorous acid in the proportion of about 0.25 to about 1.5 equivalents and, more preferably, about 0.5 to about 1.0 equivalents (chemical equivalent weight basis).
The chlorine and bromine-containing compositions are rendered more effective for the control of microorganisms by the inclusion therewith of surface active agents which may, for purposes of convenience, be referred to as "biodispersants".
When these materials are used, the amount present in the composition ranges between about 1 up to about 10% by weight.
The biodispersants are preferably chosen from the group consisting of ethylene oxide condensates with propylene oxide adducts or propylene glycol having an HLB between 4-10 and a molecular weight between 1,000-5,000, nonionic polyethoxylated straight chain alcohols, tris cyanoethylated cocodiamines, polyoxyethylene sorbitan ester/acids, nonionic N,N, dimethyl stearamides, nonionic amine polyglycol condensates, and nonionic ethoxylated alcohols.
12~9965 The Phosphonates Phosphonates which are relevant to the invention include any phosphonate which is degraded by the biocide combina-tion described, but especially:
(1) l,l~hydroxyethylidine diphosphonic acid (HEDP);
(2) tris aminomethane phosphonic acid (AMP);
Introduction The use of phosphonates for scale and corrosLon control in recirculating cooling water is widely practiced as is the use of chlorine for microbiological control. However, the use of these two practices simultaneously can cause problems. Chlorine has been demonstrated to break down many phosphonates to a significant extent. When this happens in a field application, the effectiveness of the phosphonate as a scale control agent is degraded and the orthophosphate which is a product of this reaction can contribute to scaling problems. Even some reputedly chlorine-resistant phosphonates such as l,l-hydroxyethylidine diphosphonic acid (HEDP) are not sufficiently stable for some industrial applications where continuous chlorination is practiced. Under carefully controlled conditions where the free chlorine residual is kept at a low constant level, breakdown of HEDP is minimal. However, under the less well controlled ¦
environment found in a typical plant cooling circuit, excessive chlorine levels are frequently observed. Under these conditions, HEDP or other phosphonates can break down to a sufficient degree to cause problems. Additionally, a number of dissolved ions typically found in cooling waters have been found to catalyze the breakdown of phosphonates.
The problem described above has been overcome by treating such cooling waters with sulfamic acid or other compounds ~his technoLogy is disclosed in U.S. 4,642,194-ll ~ I
. ~ '' - 2 - ~
~ - 12~9965 It has been observed that when the bioclde in cooling waters is a mixture of chlorine in combination with a bromide salt capable of releasing bromide ions, a much more profound and exaggerated degradation of the phosphonates occurs. It is an object of the invention to prevent this unexpected, rapid decomposition of phosphonates by mixtures of chlorine and bromide ions present as biocides in industrial cooling waters.
The Invention The invention is a method for preventing the decomposition of phosphonates which are present in cooling waters to prevent scale and corrosion in industrial cooling waters which also contain as a biocide the combination of chlorine and a bromide salt which releases bromide ions which comprises treating said waters with at least 1 ppm of sulfamic acid for each ppm of bromide.
The Chlorine-Bromide Biocides The biocides comprise a chlorine solution and a bromide salt capable of releasing bromide ions to the chlorine solution.
Suitable bromide salts include the alkali and alkaline earth metal bromides but are not limited thereto. For instance, magnesium bromide, calcium bromide, sodium bromide, potassium bromide, ammonium bromide, and the like salts can be used, either singly or as mixture of two or more as desired.
A bromide salt, for example, sodium bromide, when introduced into a chlorine solution in which the chlorine is present mostly as hypochlorous acid, has been shown to at least partially displace chlorine, resulting in the formation of the .
active biocide, hypobromous acid, and innoxious sodium chloride by-product as follows: ¦
NaBr~HOCl--NaCl+HOBr In present chlorination installations, the bromide salt can merely be introduced downstream of the chlorine educting water line, at which point gaseous chlorine has already been introduced into a water stream and hydrolyzed to form the hypochlorous acid and hydrochloric acid, which usually would be an acidic chlorine solution. It can also be introduced into chlorine solutions formed from sodium or calcium hypochlorite or other chlorine donors and will undergo the same reactions.
The bromide salts are themselves generally innoxious salts and thus their use in combination with chlorine presents no new or unknown hazards. Advantages of using the bromide salts along with chlorine is the formation of a more effective biocide solution due to the formation of hypobromous acid. The use of bromide salts along with chlorine for improved biocontrol effectiveness is described in detail in the following patents:
U.S. 4,451,376 and U.S. 4,643,835.
The degree of conversion of hypochlorous acid to hypobromous acid depends of course to an extent on the relative proportion of bromide salt to hypochlorous acid which are combined to form the composition and other factors affecting the displacement of chlorine with bromine.
Although the present invention encompasses any proportion of bromide salt to chlorine, in a preferred embodiment the present invention includes the combination of bromide salt to chlorine as hypochlorous acid in the proportion of about 0.25 to about 1.5 equivalents and, more preferably, about 0.5 to about 1.0 equivalents (chemical equivalent weight basis).
The chlorine and bromine-containing compositions are rendered more effective for the control of microorganisms by the inclusion therewith of surface active agents which may, for purposes of convenience, be referred to as "biodispersants".
When these materials are used, the amount present in the composition ranges between about 1 up to about 10% by weight.
The biodispersants are preferably chosen from the group consisting of ethylene oxide condensates with propylene oxide adducts or propylene glycol having an HLB between 4-10 and a molecular weight between 1,000-5,000, nonionic polyethoxylated straight chain alcohols, tris cyanoethylated cocodiamines, polyoxyethylene sorbitan ester/acids, nonionic N,N, dimethyl stearamides, nonionic amine polyglycol condensates, and nonionic ethoxylated alcohols.
12~9965 The Phosphonates Phosphonates which are relevant to the invention include any phosphonate which is degraded by the biocide combina-tion described, but especially:
(1) l,l~hydroxyethylidine diphosphonic acid (HEDP);
(2) tris aminomethane phosphonic acid (AMP);
(3) l-phosphono glycolic acid (PGA);
(4) ethylene diamine tetra(methylenephosphonic acid) (ENTP);
(5) hexamethylene diamine tetra(methylenephosphonic acid)(HMTP);
(6) diethylene triamine penta(methylenephosphonic acid):
As indicated, the phosphonates are well known mater-ials and are described in the following patents: United States 3,214,454; United States 4,026,815; United States 3,336,221;
and United States 3,278,446. They all may be used as the free acid or their water-soluble salt form.
The Sulfamic Acid 2Q The sulfamic acid may be employed as the free acid or as one of its water-soluble salts such as the sodium, potas-sium or ammonium salt.
Dosage The sulfamic acid is dosed based upon the bromide (Br) part in the cooling water. The amount used can be as ; little as 1 ppm of sulfamic acid for each ppm of bromide present.
Higher dosages within the range of 1-4 ppm may be used, al-though excellent results are achieved when the dosage is between 1-2 ppm.
12~996S
For a more complete understanding of the present invention reference is made to the attached drawings, wherein:
Figure 1 is a graph showing the effect of sulfamic acid on phosphonate stabilization in a pilot cooling tower test;
Figure 2 is a graph similar to the graph of Figure 1 but obtained under different experimental conditions.
- 6a -. i2~9965 ll Evaluation o~ the Invention The use of sulfamic acid for phosphonate stabilization was evaluated in a pilot coolin~ tower (PC~) apparatus. This device is described in the article: "Small-Scale Short-Term Methods of Evaluating Cooling Water Treatments...Are They Worthwhile?", D. T. Reed and R. Nass, Nalco Chemical Company, International Water Conference, Pittsburgh, PA, Nov. 4-6, 1975.
Two PCT tests were used to evaluate the invention.
Objectives of the tests were to determine:
1) the decomposition of phosphonate by bromine in the absence of stabilizer;
2) the effect of sulfamic acid in reducing the decomposition.
Experimental Procedures The composition of water used in the pilot cooling tower tests was four concentration synthetic lake water. Concentration ratio of tower water was held constant by a conductivity controller. Cooling water pH was controlled by 9.û+ 0.2 using dilute H2S04 feed and a pH controller. Chlorine was introduced into the system using diluted mixtures of 5.25% sodium hypochlorite at feed rates necessary to maintain a 0.1-0.2 ppm free residual. A scale control program containing 6% HEDP for scale control was fed to the tower at rates proportional to blowdown to maintain a constant theoretical level of HEDP in the tower water. Based on daily tower water analyses, HEDP feed rates were adjusted as necessary to maintain the desired level of ` 12~?9965 HEDP. Two separate PCT tests were conducted. Each test included three phases:
1. Baseline decomposition: Feed sodium hypochlorite to maintain a 0.1 to 0.2 ppm free residual and deter~ine HEDP decomposition from daily phosphate analyses.
2. Bromine induced decomposition: Introduce sodium bromide feed and determine effect on HEDP and orthophosphate levels.
3. Stabilization: Once a steady state level of bromine HEDP decomposition was obtained, feed sulfamic acid and determine effect on HEDP and orthophosphate levels.
Results and Discussion Results from the two pilot cooling tower tests are shown in Fig. 1 and Fig. 2. In test number one, the first week of the experiment was used to establish ~aseline decomposition. On day seven, 10 ppm sodium bromide feed (8 ppm as Br ) was initiated and immediately phosphonate decomposition increased reaching a steady state of approximately 25%. 10 ppm sulfamic acid feed was then introduced and, after an initial reduction in chlorine feed to maintain the desired 0.1-0.2 ppm free residual, phosphonate decomposition immediately fell. The test was discontinued one week following the start of stabilizer feed.
Fig. 2 shows results obtained in the second PCT
stabilization tests. As shown in Fig. 2, only the latter two weeks of the test were used for evaluation of the present invention. In this test, days 9-13 were used to establish ~ 12~9965 baseline decomposition, days 13-16 sodium bromide and sulfamic acid were fed, and for the final five (5) days of the test, sodium bromide alone was fed with hypochlorite. As in the first PCT test, the combination of chlorine and bromine resulted in significantly higher levels of phosphonate decomposition.
Table I below summarizes the PCT test results and clearly shows the efficacy of sulfamic acid in reducing phosphonate decomposition.
Table I
Pilot Cooling Tower Bromine Phosphonate Decomposition - Summary 1 Treatment Free Halogen Biocide Duration Residual ~ Phosphonate Feed (Oays) (ppm) Degradation NaOCl 5 0.13 + 0.07 12.9 + 8.5 NaOCl 9 0.04 + 0.06 (Chlorine) 28.3 + 12.2 NaBr 0.14 + 0.06 (Bromine) NaOCl 6 0.05 + 0.05 (Chlorine) 14.3 _ 3.9 NaBr 0.08 + 0.03 (Bromine) Sulfamic Acid 1 Phosphonate - HEDP
NaBr Feed - 8 ppm as Br~
Sulfamic Acid Feed - 10 ppm
As indicated, the phosphonates are well known mater-ials and are described in the following patents: United States 3,214,454; United States 4,026,815; United States 3,336,221;
and United States 3,278,446. They all may be used as the free acid or their water-soluble salt form.
The Sulfamic Acid 2Q The sulfamic acid may be employed as the free acid or as one of its water-soluble salts such as the sodium, potas-sium or ammonium salt.
Dosage The sulfamic acid is dosed based upon the bromide (Br) part in the cooling water. The amount used can be as ; little as 1 ppm of sulfamic acid for each ppm of bromide present.
Higher dosages within the range of 1-4 ppm may be used, al-though excellent results are achieved when the dosage is between 1-2 ppm.
12~996S
For a more complete understanding of the present invention reference is made to the attached drawings, wherein:
Figure 1 is a graph showing the effect of sulfamic acid on phosphonate stabilization in a pilot cooling tower test;
Figure 2 is a graph similar to the graph of Figure 1 but obtained under different experimental conditions.
- 6a -. i2~9965 ll Evaluation o~ the Invention The use of sulfamic acid for phosphonate stabilization was evaluated in a pilot coolin~ tower (PC~) apparatus. This device is described in the article: "Small-Scale Short-Term Methods of Evaluating Cooling Water Treatments...Are They Worthwhile?", D. T. Reed and R. Nass, Nalco Chemical Company, International Water Conference, Pittsburgh, PA, Nov. 4-6, 1975.
Two PCT tests were used to evaluate the invention.
Objectives of the tests were to determine:
1) the decomposition of phosphonate by bromine in the absence of stabilizer;
2) the effect of sulfamic acid in reducing the decomposition.
Experimental Procedures The composition of water used in the pilot cooling tower tests was four concentration synthetic lake water. Concentration ratio of tower water was held constant by a conductivity controller. Cooling water pH was controlled by 9.û+ 0.2 using dilute H2S04 feed and a pH controller. Chlorine was introduced into the system using diluted mixtures of 5.25% sodium hypochlorite at feed rates necessary to maintain a 0.1-0.2 ppm free residual. A scale control program containing 6% HEDP for scale control was fed to the tower at rates proportional to blowdown to maintain a constant theoretical level of HEDP in the tower water. Based on daily tower water analyses, HEDP feed rates were adjusted as necessary to maintain the desired level of ` 12~?9965 HEDP. Two separate PCT tests were conducted. Each test included three phases:
1. Baseline decomposition: Feed sodium hypochlorite to maintain a 0.1 to 0.2 ppm free residual and deter~ine HEDP decomposition from daily phosphate analyses.
2. Bromine induced decomposition: Introduce sodium bromide feed and determine effect on HEDP and orthophosphate levels.
3. Stabilization: Once a steady state level of bromine HEDP decomposition was obtained, feed sulfamic acid and determine effect on HEDP and orthophosphate levels.
Results and Discussion Results from the two pilot cooling tower tests are shown in Fig. 1 and Fig. 2. In test number one, the first week of the experiment was used to establish ~aseline decomposition. On day seven, 10 ppm sodium bromide feed (8 ppm as Br ) was initiated and immediately phosphonate decomposition increased reaching a steady state of approximately 25%. 10 ppm sulfamic acid feed was then introduced and, after an initial reduction in chlorine feed to maintain the desired 0.1-0.2 ppm free residual, phosphonate decomposition immediately fell. The test was discontinued one week following the start of stabilizer feed.
Fig. 2 shows results obtained in the second PCT
stabilization tests. As shown in Fig. 2, only the latter two weeks of the test were used for evaluation of the present invention. In this test, days 9-13 were used to establish ~ 12~9965 baseline decomposition, days 13-16 sodium bromide and sulfamic acid were fed, and for the final five (5) days of the test, sodium bromide alone was fed with hypochlorite. As in the first PCT test, the combination of chlorine and bromine resulted in significantly higher levels of phosphonate decomposition.
Table I below summarizes the PCT test results and clearly shows the efficacy of sulfamic acid in reducing phosphonate decomposition.
Table I
Pilot Cooling Tower Bromine Phosphonate Decomposition - Summary 1 Treatment Free Halogen Biocide Duration Residual ~ Phosphonate Feed (Oays) (ppm) Degradation NaOCl 5 0.13 + 0.07 12.9 + 8.5 NaOCl 9 0.04 + 0.06 (Chlorine) 28.3 + 12.2 NaBr 0.14 + 0.06 (Bromine) NaOCl 6 0.05 + 0.05 (Chlorine) 14.3 _ 3.9 NaBr 0.08 + 0.03 (Bromine) Sulfamic Acid 1 Phosphonate - HEDP
NaBr Feed - 8 ppm as Br~
Sulfamic Acid Feed - 10 ppm
Claims (2)
1. A method for preventing the decomposition of phos-phonates which are present in cooling waters to prevent scale and corrosion in industrial cooling waters which also contain as a biocide the combination of chlorine and a bromide salt which releases bromide ions which comprises treating said waters with at least 1 ppm of sulfamic acid for each ppm of bromide.
2. The method of Claim 1 wherein the phosphonate is 1,1-hydroxyethylidine diphosphonic acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/108,657 US4759852A (en) | 1987-10-15 | 1987-10-15 | Use of sulfamic acid to inhibit phosphonate decomposition by chlorine-bromine mixtures |
| US108,657 | 1987-10-15 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1299965C true CA1299965C (en) | 1992-05-05 |
Family
ID=22323409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000579721A Expired - Fee Related CA1299965C (en) | 1987-10-15 | 1988-10-11 | Use of sulfamic acid to inhibit phosphonate decomposition by chlorine-bromine mixtures |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US4759852A (en) |
| EP (1) | EP0311954A3 (en) |
| JP (1) | JPH01130795A (en) |
| AU (1) | AU601134B2 (en) |
| CA (1) | CA1299965C (en) |
| NZ (1) | NZ226436A (en) |
| ZA (1) | ZA887651B (en) |
Families Citing this family (52)
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| US4929424A (en) * | 1988-04-11 | 1990-05-29 | Nalco Chemical Company | Prevention of vapor phase corrosion caused by halogens in brewery pasteurizers |
| US4883600A (en) * | 1988-10-12 | 1989-11-28 | Nalco Chemical Company | Stabilization of soluble manganese in aqueous systems |
| US5688515A (en) * | 1989-06-16 | 1997-11-18 | Occidental Chemical Corporation | Hypochlorite donor/bromide ion donor tablets which are stable in water |
| EP0429631B1 (en) * | 1989-06-16 | 1993-07-28 | University Of Houston | Biocidal methods for recirculating water systems |
| US4992209A (en) * | 1989-10-26 | 1991-02-12 | Nalco Chemical Company | Method for inhibiting corrosion in cooling systems and compositions therefor, containing a nitrite corrosion inhibitor and bromosulfamate |
| US5141652A (en) * | 1990-04-18 | 1992-08-25 | Ethyl Corporation | Water treatment process |
| AU1281792A (en) * | 1991-04-08 | 1992-10-15 | Ciba-Geigy Ag | Method for scale, corrosion and microbiological control in aqueous systems |
| US5516501A (en) * | 1992-05-05 | 1996-05-14 | International Dioxcide | Process for the preparation of aqueous solutions of bromine based disinfectants |
| US5439611A (en) * | 1992-05-07 | 1995-08-08 | Calgon Corporation | Stabilization of hydroxyalkylidene phosphonate scale inhibitors against degradation by bromine and chlorine biocides |
| US5449476A (en) * | 1992-05-07 | 1995-09-12 | Calgon Corporation | Stabilization of aminomethylene phosphonate scale inhibitors against degradation by bromine and chlorine biocides |
| US5433886A (en) * | 1992-05-07 | 1995-07-18 | Calgon Corporation | Stabilization of polyether polyamino methylene phosphonate scale inhibitors against degradation by bromine and chlorine biocides |
| US5795487A (en) * | 1997-01-03 | 1998-08-18 | Nalco Chemical Company | Process to manufacture stabilized alkali or alkaline earth metal hypobromite and uses thereof in water treatment to control microbial fouling |
| US5624575A (en) * | 1995-04-28 | 1997-04-29 | Nalco Chemical Company | Method for preventing microbial deposits in the papermaking process with ethylene oxide/propylene oxide copolymers |
| US5683654A (en) * | 1996-03-22 | 1997-11-04 | Nalco Chemical Co | Process to manufacture stabilized alkali or alkaline earth metal hypobromite and uses thereof in water treatment to control microbial fouling |
| JPH11506139A (en) * | 1996-03-22 | 1999-06-02 | ナルコ ケミカル カンパニー | Stabilized alkali or alkaline earth metal hypobromite and process for producing the same |
| US5942126A (en) * | 1997-01-03 | 1999-08-24 | Nalco Chemical Company | Process to manufacture stabilized alkali or alkaline earth metal hypobromite and uses thereof in water treatment to control microbial fouling |
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| US8293795B1 (en) | 1998-06-01 | 2012-10-23 | Albemarle Corporation | Preparation of concentrated aqueous bromine solutions and biocidal applications thereof |
| US6511682B1 (en) | 1998-06-01 | 2003-01-28 | Albemarle Corporation | Concentrated aqueous bromine solutions and their preparation |
| US6068861A (en) * | 1998-06-01 | 2000-05-30 | Albemarle Corporation | Concentrated aqueous bromine solutions and their preparation |
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| US6652889B2 (en) * | 1998-06-01 | 2003-11-25 | Albemarle Corporation | Concentrated aqueous bromine solutions and their preparation and use |
| US8414932B2 (en) | 1998-06-01 | 2013-04-09 | Albemarie Corporation | Active bromine containing biocidal compositions and their preparation |
| US6299909B1 (en) | 1998-06-01 | 2001-10-09 | Albemarle Corporation | Concentrated aqueous bromine solutions and their preparation |
| US6352725B1 (en) | 1998-06-01 | 2002-03-05 | Albemarle Corporation | Continuous processes for preparing concentrated aqueous liquid biocidal composition |
| US6348219B1 (en) | 1998-06-01 | 2002-02-19 | Albemarle Corporation | Processes for preparing concentrated aqueous liquid biocidal compositions |
| US6287473B1 (en) | 1998-06-29 | 2001-09-11 | Nalco Chemical Company | Stable oxidizing bromine formulations, method of manufacture and uses thereof for biofouling control |
| US6156229A (en) | 1998-06-29 | 2000-12-05 | Nalco Chemical Company | Stable oxidizing bromine formulations, method of manufacture and uses thereof for biofouling control |
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| DE19837068A1 (en) | 1998-08-17 | 2000-02-24 | Bayer Ag | Water treatment composition, especially for use in cooling circuits, comprises polyaspartic acid, biocidal oxidizing agent and sulfamic acid stabilizer |
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| BE579012A (en) * | 1958-09-06 | 1900-01-01 | ||
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| US4643835A (en) * | 1985-08-28 | 1987-02-17 | Nalco Chemical Company | Asiatic clam control chemical |
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| US4711724A (en) * | 1985-09-16 | 1987-12-08 | Nalco Chemical Company | Method for prevention of phosphonate decomposition by chlorine |
| EP0228593A3 (en) * | 1985-12-10 | 1989-10-18 | Chesebrough-Pond's Inc. | Composition for cleaning water-containing devices |
| US4671934A (en) * | 1986-04-18 | 1987-06-09 | Buckman Laboratories, Inc. | Aminophosphonic acid/phosphate mixtures for controlling corrosion of metal and inhibiting calcium phosphate precipitation |
| AU612603B2 (en) * | 1986-11-13 | 1991-07-18 | B.F. Goodrich Company, The | Calcium phosphonate scale inhibition |
-
1987
- 1987-10-15 US US07/108,657 patent/US4759852A/en not_active Expired - Lifetime
-
1988
- 1988-10-03 NZ NZ226436A patent/NZ226436A/en unknown
- 1988-10-05 AU AU23430/88A patent/AU601134B2/en not_active Ceased
- 1988-10-10 EP EP88116786A patent/EP0311954A3/en not_active Withdrawn
- 1988-10-11 CA CA000579721A patent/CA1299965C/en not_active Expired - Fee Related
- 1988-10-12 JP JP63255029A patent/JPH01130795A/en active Pending
- 1988-10-13 ZA ZA887651A patent/ZA887651B/en unknown
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|---|---|
| AU601134B2 (en) | 1990-08-30 |
| JPH01130795A (en) | 1989-05-23 |
| NZ226436A (en) | 1989-10-27 |
| US4759852A (en) | 1988-07-26 |
| EP0311954A3 (en) | 1989-06-07 |
| AU2343088A (en) | 1989-04-20 |
| EP0311954A2 (en) | 1989-04-19 |
| ZA887651B (en) | 1989-07-26 |
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