WO2004078662A1 - Scale inhibitor - Google Patents
Scale inhibitor Download PDFInfo
- Publication number
- WO2004078662A1 WO2004078662A1 PCT/GB2004/000842 GB2004000842W WO2004078662A1 WO 2004078662 A1 WO2004078662 A1 WO 2004078662A1 GB 2004000842 W GB2004000842 W GB 2004000842W WO 2004078662 A1 WO2004078662 A1 WO 2004078662A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- aqueous system
- silica
- compound
- aqueous
- scale
- Prior art date
Links
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
- C02F5/086—Condensed phosphates
-
- 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
- C02F5/02—Softening water by precipitation of the hardness
-
- 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
- C02F5/02—Softening water by precipitation of the hardness
- C02F5/04—Softening water by precipitation of the hardness using phosphates
-
- 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
- C02F5/145—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 combined with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/023—Water in cooling circuits
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/26—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof
- C02F2103/28—Nature of the water, waste water, sewage or sludge to be treated from the processing of plants or parts thereof from the paper or cellulose industry
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
- C02F2103/365—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds from petrochemical industry (e.g. refineries)
-
- 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
Definitions
- This invention relates to a method of inhibiting fouling by silica and silicates in aqueous systems and, in particular, to the use of phosphorus containing compounds to inhibit the deposition of silica and silicate scales on surfaces.
- Scale inhibitors are used to treat a variety of aqueous systems such as boiler water, industrial process water, cooling water and water in central heating and air conditioning systems, to prevent deposition of calcium carbonate, or other alkaline earth metal scale from hard water systems.
- silica is now a major fouling problem in aqueous systems. Silica is difficult to inhibit as it assumes low solubility forms depending on the conditions in the aqueous system. For example, below pH 7 monomeric silica tends to polymerize to form oligomeric or colloidal silica. At pH's above 7, for example, pH 9.5, silica can form a monomeric silicate ion. As conversion of silica into these various forms can be slow, various forms of silica can co-exist in an aqueous system at any one time, depending on the history of the system.
- Silicate ions can react with polyvalent cations, such as magnesium and calcium, to produce salts with limited solubility.
- polyvalent cations such as magnesium and calcium
- Silicate ions can react with polyvalent cations, such as magnesium and calcium, to produce salts with limited solubility.
- a mixture of forms of silica it is common for a mixture of forms of silica to be present: monomeric, oligomeric and colloidal silica; magnesium silicate, calcium silicate and other silicate salts.
- Silica scale inhibitors are known per se from EP 0 459 661. It is an object of the present invention to ameliorate silica and/or silicate fouling of aqueous systems.
- the known scale inhibitors such as those disclosed in EP 0 861 846 B, EP 0 491 391 B and WO 00/18695 have improved properties for the control of silica and silicate fouling in aqueous systems over current silica/silicate scale inhibitors.
- the present invention provides a method of inhibiting silica and silicate scale in aqueous systems, which method comprises the addition to the aqueous system of a scale inhibiting amount of a phosphorus-containing additive, the additive being selected from at least one or more of:
- X is H or an alkaline metal, alkaline earth or other polyvalent metal, ammonium or an organic base
- n is the valency of X
- R is a polymeric chain comprising between 1 and 100,000 groups derived from at least one unsaturated compound in which the multiple bond is activated chemically by an adjacent electron withdrawing group
- Y and Z which may be the same or different, are each hydrogen, a PO 3 X 2 , SO 3 X or CO 2 X group or an alkyl or aryl moiety; (2) a compound comprising ring opened ethanolamine bis (methylene phosphonate) or one or more N-oxides thereof;
- the phosphorus-containing additives may be added to said aqueous system at a concentration of from between 0.1 to 1000 ppm.
- the aqueous system may be, for example:
- aqueous system used in the desalination of water a method of desalination is selected from one or more of:
- the present invention also provides phosphorus-containing additives for use as silica and/or silicate scale inhibitors in aqueous systems, in accordance with the method hereinabove described.
- silica and silicate scale inhibition of phosphorus containing compounds were employed, in accordance with the present invention, compared with other scale inhibitors.
- silicate scale inhibitor a terpolymer of acrylic acid, 2-acrylamido-2- methylpropanesulphonic acid and tertiary-butylacrylamide - hereafter referred to as AA/ AMPS/t-BAm
- the pH of this solution was adjusted to 8.5 at 25 2 C with HC1 and stored in a sealed container for at least one week before the test.
- the pH of the mix was then adjusted to 8.0 ⁇ 0.05 at 25 S C by the addition of 0.1M HC1 via an "Autotitrator" .
- the test solution was then transferred to a polyethylene bottle and placed in a thermostatic water bath at 70 2 C for a period of 30 minutes. After this time the bottle was removed and allowed to cool for one hour before the contents were filtered through a 0.45 micron 'Millipore' filter.
- concentrations of silicon, calcium and magnesium remaining in solution were then determined by Inductively Coupled Plasma spectroscopy (ICP) .
- ICP Inductively Coupled Plasma spectroscopy
- A Acrylic acid
- HPA Hydroxypropyl acrylate
- HPMA Hydroxypropyl methacrylate
- MAA Methacrylic acid
- VS Vinyl sulphonate
- VSA Vinyl sulphonic acid
- VDPA Vinyl diphosphonic acid
- PPE l-Phosphono-2-phosphinoethane
- DPPE l,l-Diphosphono-2-phosphinoethane
- AMPS 2-Acrylamido-2-methlypropane sulphonic acid
- t-BAm Tertiary butyl acrylamide
- compounds in accordance with the present invention are superior silica/silicate scale inhibitors when compared with a known silica/silicate scale inhibitor (AA/AMPS/t-BAm) .
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a method of inhibiting silica and silicate scale in aqueous systems. The method comprises the addition to the aqueous system of a scale inhibiting amount of a phosphorus containing additive. The additive is selected from one or more of an oligomer or polymer having phosphorus containing end caps; compounds comprising ring opened ethanolamine bis (methylene phosphonate) or N oxides thereof; an oligomer which is soluble in water and a compound having one or more phosphino- or phosphono-carboxylate groups.
Description
SCALE INHIBITOR
This invention relates to a method of inhibiting fouling by silica and silicates in aqueous systems and, in particular, to the use of phosphorus containing compounds to inhibit the deposition of silica and silicate scales on surfaces.
Scale inhibitors are used to treat a variety of aqueous systems such as boiler water, industrial process water, cooling water and water in central heating and air conditioning systems, to prevent deposition of calcium carbonate, or other alkaline earth metal scale from hard water systems.
However, although other types of scale, for example calcium carbonate or barium sulphate scale, are well controlled, silica is now a major fouling problem in aqueous systems. Silica is difficult to inhibit as it assumes low solubility forms depending on the conditions in the aqueous system. For example, below pH 7 monomeric silica tends to polymerize to form oligomeric or colloidal silica. At pH's above 7, for example, pH 9.5, silica can form a monomeric silicate ion. As conversion of silica into these various forms can be slow, various forms of silica can co-exist in an aqueous system at any one time, depending on the history of the system.
Silicate ions can react with polyvalent cations, such as magnesium and calcium, to produce salts with limited solubility. Thus in aqueous systems it is common for a mixture of forms of silica to be present: monomeric, oligomeric and colloidal silica; magnesium silicate, calcium silicate and other silicate salts.
Silica scale inhibitors are known per se from EP 0 459 661.
It is an object of the present invention to ameliorate silica and/or silicate fouling of aqueous systems. However, the applicants have now found that the known scale inhibitors such as those disclosed in EP 0 861 846 B, EP 0 491 391 B and WO 00/18695 have improved properties for the control of silica and silicate fouling in aqueous systems over current silica/silicate scale inhibitors.
Accordingly, the present invention provides a method of inhibiting silica and silicate scale in aqueous systems, which method comprises the addition to the aqueous system of a scale inhibiting amount of a phosphorus-containing additive, the additive being selected from at least one or more of:
(1) an oligomer or polymer having phosphorus containing end caps having the general formula:
wherein X is H or an alkaline metal, alkaline earth or other polyvalent metal, ammonium or an organic base, n is the valency of X, and R is a polymeric chain comprising between 1 and 100,000 groups derived from at least one unsaturated compound in which the multiple bond is activated chemically by an adjacent electron withdrawing group, and Y and Z, which may be the same or different, are each hydrogen, a PO3X2, SO3X or CO2X group or an alkyl or aryl moiety;
(2) a compound comprising ring opened ethanolamine bis (methylene phosphonate) or one or more N-oxides thereof;
(3) a compound comprising an oligomer of the formula H[CHCO2MCHCO2M]nPO3M2 wherein M is a cation such that the compound is soluble in water, and n is greater than 1; and
(4) a compound having one or more phosphino- or phosphono- carboxylate groups.
The phosphorus-containing additives may be added to said aqueous system at a concentration of from between 0.1 to 1000 ppm.
The aqueous system may be, for example:
1) used in a cooling tower;
2) used in a boiler;
3) used in the production of sugar;
4) used in enhanced oil recovery;
5) used in geothermal processes;
6) used in detergent applications; or
7) used in the desalination of water.
8) used in paper manufacture.
When the aqueous system is used in the desalination of water a method of desalination is selected from one or more of:
Multi-stage Flash; Multi-effect Distillation;
Vapour Compression; Reverse Osmosis; Dialysis; Hyperfiltration; Nanofiltration; and
Freezing
The present invention also provides phosphorus-containing additives for use as silica and/or silicate scale inhibitors in aqueous systems, in accordance with the method hereinabove described.
The present invention will now be illustrated, merely by way of example, as follows:
Evaluation of Silica/Silicate Scale Inhibitors
The following test was employed to demonstrate the improved property of silica and silicate scale inhibition of phosphorus containing compounds, in accordance with the present invention, compared with other scale inhibitors. In particular, comparison was made between a known silicate scale inhibitor (a terpolymer of acrylic acid, 2-acrylamido-2- methylpropanesulphonic acid and tertiary-butylacrylamide - hereafter referred to as AA/ AMPS/t-BAm) .
Method
A high silica water was prepared by mixing together 50 ml each of solutions (A) and (B), which were prepared from Analytical Reagent grade chemicals (unless otherwise stated) :
(A) 'Anion Solution'
Sodium silicate solution, 27% (Tech.) - 4.863 g/1
Sodium hydrogen carbonate - 1.017 g/1
The pH of this solution was adjusted to 8.5 at 252C with HC1 and stored in a sealed container for at least one week before the test.
(B) 'Cation Solution'
Calcium chloride dihydrate - 0.890 g/1 Magnesium chloride hexahydrate - 1.231 g/1
1 ml of the candidate inhibitor solution (1% active) was added to solution (A) prior to the addition of solution (B). In the case of the 'Blank' , 1 ml of deionised water was substituted for the inhibitor solution. This results in a medium having the following composition:
Si - 650 mg/1 as SiO2 Ca - 300 mg/1 as CaCO3 Mg - 300 mg/1 as CaCO3 HCO3 - 300 mg/1 as CaCO3 Inhibitor - 100 mg/1 as active
The pH of the mix was then adjusted to 8.0 ± 0.05 at 25SC by the addition of 0.1M HC1 via an "Autotitrator" . The test solution was then transferred to a polyethylene bottle and placed in a thermostatic water bath at 702C for a period of 30 minutes. After this time the bottle was
removed and allowed to cool for one hour before the contents were filtered through a 0.45 micron 'Millipore' filter. The concentrations of silicon, calcium and magnesium remaining in solution were then determined by Inductively Coupled Plasma spectroscopy (ICP) .
Performance, with respect to silica/silicate inhibition, was then determined by use of the formula:
% Inhibition = [Si(inhib) - Si(blank)] / [Si(initial) - Si(blank)] x 100
The results are tabulated below.
Key: A A = Acrylic acid
HPA = Hydroxypropyl acrylate HPMA = Hydroxypropyl methacrylate MAA = Methacrylic acid VS = Vinyl sulphonate VSA= Vinyl sulphonic acid
VDPA = Vinyl diphosphonic acid PPE = l-Phosphono-2-phosphinoethane DPPE = l,l-Diphosphono-2-phosphinoethane AMPS = 2-Acrylamido-2-methlypropane sulphonic acid t-BAm = Tertiary butyl acrylamide
As can be seen from the results, compounds in accordance with the present invention are superior silica/silicate scale inhibitors when compared with a known silica/silicate scale inhibitor (AA/AMPS/t-BAm) .
Claims
1. A method of inhibiting silica and silicates scale in aqueous systems, which method comprises the addition to the aqueous system of a scale inhibiting amount of a phosphorus containing additive, the additive being selected from at least one or more of:
(1) an oligomer or polymer having phosphorus containing end caps and having the general formula:
wherein X is H or an alkaline metal, alkaline earth or other polyvalent metal, ammonium or an organic base, n is the valency of X, and R is a polymeric chain comprising between 1 and 100,000 groups derived from at least one unsaturated compound in which the multiple bond is activated chemically by an adjacent electron withdrawing group, and Y and Z, which may be the same or different, are each hydrogen, a PO3X2, SO3X or CO2X group or an alkyl or aryl moiety;
(2) a compound comprising ring opened ethanolamine bis (methylene phosphonate) or one or more N-oxides thereof;
(3) a compound comprising an oligomer of the formula H[CHCO2MCHCO2M]nPO3M2 wherein M is a cation such that the compound is soluble in water, and n is greater than 1 ; and (4) a compound having one or more phosphino- or phosphono- carboxylate groups.
2. A method as claimed in claim 1, wherein the phosphorus containing additives are added to said aqueous system at a concentration of from between 0.1 to 1000 ppm.
3. A method as claimed in claim 1 or claim 2, wherein the aqueous system is used in a cooling tower.
4. A method according to claim 1 or claim 2, in which the aqueous system is used in a boiler.
5. A method as claimed in claim 1 or claim 2, in which the aqueous system is used in the production of sugar.
6. A method as claimed in claim 1 or claim 2, in which the aqueous system is used in enhanced oil recovery.
7. A method as claimed in claim 1 or claim 2, in which the aqueous system is used in geothermal processes; .
8. A method as claimed in claim 1 or claim 2, in which the aqueous system is used in detergent applications.
9. A method as claimed in claim 1 or claim 2, in which the aqueous system is used in the desalination of water.
10. A method as claimed in claim 1 or claim 2, in which the aqueous system is used in paper manufacture.
11. A method as claimed in claim 9 in which a method of desalination is selected from one or more of:
Multi-stage Flash; Multi-effect Distillation;
Vapour Compression; Reverse Osmosis; Dialysis; Hyperfiltration; Nanofiltration; and
Freezing
12. A phosphorus-containing additive for use as a silica and/or silicate scale inhibitor in aqueous systems, in accordance with the method of any one of the preceding claims.
13. A phosphorus-containing additive, substantially as described herein and with reference to the example.
14. A method of inhibiting silica and silicate scale in aqueous systems, substantially as described herein.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0305202.4 | 2003-03-07 | ||
| GB0305202A GB0305202D0 (en) | 2003-03-07 | 2003-03-07 | Scale inhibitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2004078662A1 true WO2004078662A1 (en) | 2004-09-16 |
Family
ID=9954282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/GB2004/000842 WO2004078662A1 (en) | 2003-03-07 | 2004-03-01 | Scale inhibitor |
Country Status (3)
| Country | Link |
|---|---|
| GB (1) | GB0305202D0 (en) |
| TW (1) | TW200503972A (en) |
| WO (1) | WO2004078662A1 (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006051420A1 (en) * | 2004-11-10 | 2006-05-18 | Danisco A/S | Antibacterial composition and methods thereof |
| GB2436107A (en) * | 2005-03-29 | 2007-09-19 | Rhodia Uk Ltd | Inhibiting silica and silicate scale in aqueous systems |
| GB2455776A (en) * | 2007-12-21 | 2009-06-24 | Rhodia Operations | Scale inhibition |
| US8002119B2 (en) | 2006-02-08 | 2011-08-23 | Basf Se | Control of the thickening of silicate-containing aqueous systems |
| US20160177233A1 (en) * | 2014-12-22 | 2016-06-23 | Ecolab Usa Inc. | Warewashing composition containing alkanol amine phosphonate and methods of use |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0459661A1 (en) * | 1990-05-23 | 1991-12-04 | Rohm And Haas Company | Silica scale inhibition |
| EP0508953A1 (en) * | 1991-04-08 | 1992-10-14 | Fmc Corporation (Uk) Limited | Method for scale, corrosion and microbiological control in aqueous systems |
| EP0491391B1 (en) * | 1990-12-18 | 1996-05-08 | ALBRIGHT & WILSON UK LIMITED | Water treatment agent |
| WO2000018695A2 (en) * | 1998-09-30 | 2000-04-06 | Albright & Wilson Uk Limited | Water treatment |
| US6090345A (en) * | 1998-02-03 | 2000-07-18 | Bayer Ag | Phosphorus-containing compounds based on 1-hydroxypropane-1, 3-diphosphonic acid |
| EP0861846B1 (en) * | 1997-02-26 | 2003-04-02 | Rhodia Consumer Specialties Limited | Novel phosphino derivatives |
-
2003
- 2003-03-07 GB GB0305202A patent/GB0305202D0/en not_active Ceased
-
2004
- 2004-03-01 WO PCT/GB2004/000842 patent/WO2004078662A1/en active Application Filing
- 2004-03-05 TW TW93105899A patent/TW200503972A/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0459661A1 (en) * | 1990-05-23 | 1991-12-04 | Rohm And Haas Company | Silica scale inhibition |
| EP0491391B1 (en) * | 1990-12-18 | 1996-05-08 | ALBRIGHT & WILSON UK LIMITED | Water treatment agent |
| EP0508953A1 (en) * | 1991-04-08 | 1992-10-14 | Fmc Corporation (Uk) Limited | Method for scale, corrosion and microbiological control in aqueous systems |
| EP0861846B1 (en) * | 1997-02-26 | 2003-04-02 | Rhodia Consumer Specialties Limited | Novel phosphino derivatives |
| US6090345A (en) * | 1998-02-03 | 2000-07-18 | Bayer Ag | Phosphorus-containing compounds based on 1-hydroxypropane-1, 3-diphosphonic acid |
| WO2000018695A2 (en) * | 1998-09-30 | 2000-04-06 | Albright & Wilson Uk Limited | Water treatment |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006051420A1 (en) * | 2004-11-10 | 2006-05-18 | Danisco A/S | Antibacterial composition and methods thereof |
| US7354888B2 (en) | 2004-11-10 | 2008-04-08 | Danisco A/S | Antibacterial composition and methods thereof comprising a ternary builder mixture |
| GB2436107A (en) * | 2005-03-29 | 2007-09-19 | Rhodia Uk Ltd | Inhibiting silica and silicate scale in aqueous systems |
| US8002119B2 (en) | 2006-02-08 | 2011-08-23 | Basf Se | Control of the thickening of silicate-containing aqueous systems |
| GB2455776A (en) * | 2007-12-21 | 2009-06-24 | Rhodia Operations | Scale inhibition |
| US20160177233A1 (en) * | 2014-12-22 | 2016-06-23 | Ecolab Usa Inc. | Warewashing composition containing alkanol amine phosphonate and methods of use |
| US9765286B2 (en) * | 2014-12-22 | 2017-09-19 | Ecolab Usa Inc. | Warewashing composition containing alkanol amine phosphonate and methods of use |
| US10487295B2 (en) | 2014-12-22 | 2019-11-26 | Ecolab Usa Inc. | Warewashing composition containing alkanol amine phosphonate and methods of use |
Also Published As
| Publication number | Publication date |
|---|---|
| GB0305202D0 (en) | 2003-04-09 |
| TW200503972A (en) | 2005-02-01 |
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