US20060102563A1 - Treating slurries - Google Patents

Treating slurries Download PDF

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Publication number
US20060102563A1
US20060102563A1 US10/542,432 US54243205A US2006102563A1 US 20060102563 A1 US20060102563 A1 US 20060102563A1 US 54243205 A US54243205 A US 54243205A US 2006102563 A1 US2006102563 A1 US 2006102563A1
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US
United States
Prior art keywords
slurry
tetrakis
hydroxymethyl
phosphonium
salt
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.)
Abandoned
Application number
US10/542,432
Inventor
Christopher Jones
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay Solutions UK Ltd
Original Assignee
Rhodia Consumer Specialties Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Rhodia Consumer Specialties Ltd filed Critical Rhodia Consumer Specialties Ltd
Assigned to RHODIA CONSUMER SPECIALTIES LIMITED reassignment RHODIA CONSUMER SPECIALTIES LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: JONES, CHRISTOPHER RAYMOND
Publication of US20060102563A1 publication Critical patent/US20060102563A1/en
Priority to US13/586,012 priority Critical patent/US20120309718A1/en
Priority to US13/856,058 priority patent/US8772356B2/en
Priority to US14/285,973 priority patent/US20140256686A1/en
Priority to US15/412,800 priority patent/US20170127681A1/en
Abandoned legal-status Critical Current

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Classifications

    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/34Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-halogen bonds; Phosphonium salts
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B16/00Use of organic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of organic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02Compounds of alkaline earth metals or magnesium
    • C09C1/021Calcium carbonates
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40Compounds of aluminium
    • C09C1/42Clays
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09CTREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C3/00Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08Treatment with low-molecular-weight non-polymer organic compounds
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/80Compositional purity

Definitions

  • This invention relates to a composition for treating inorganic slurries and to a method of treating inorganic slurries with the aforesaid composition so as to maintain the slurries in a substantially homogeneous phase.
  • inorganic slurries contain about 70% to 80% by weight of solids.
  • Many inorganic slurries are known to be susceptible to bacterial contamination and it has been the practice to add one or more biocidally-active materials to the slurries in order to minimise such contamination.
  • Phosphorus-containing compounds in particular tetrakis(hydroxyorgano)phosphonium salts (THP + salts) are known to be effective biocides.
  • THP + salts tetrakis(hydroxyorgano)phosphonium salts
  • Experimental work carried out by the applicants has shown, for example, that the addition of a solution of tetrakis(hydroxymethyl)phosphonium sulphate (THPS) to a calcium carbonate-based slurry can give rise to a reduction in bacterial count of 10 4 in 2 hours.
  • THPS tetrakis(hydroxymethyl)phosphonium sulphate
  • composition comprising a THP + salt and a dispersant will provide continuing preservation against bacterial contamination, while at the same time maintaining the slurry in a substantially homogeneous phase.
  • the present invention provides a composition for treating an inorganic slurry, the composition comprising:
  • the THP + salt is preferably tetrakis(hydroxymethyl)phosphonium sulphate.
  • the THP + salt may be tetrakis(hydroxymethyl)phosphonium chloride, phosphate, nitrate or oxalate.
  • a preferred example of a dispersant of the type (b)(i) is a compound having one tertiary nitrogen atom, such as a sodium salt of nitrilo-tris(methylene phosphate), particularly the tetra-sodium salt.
  • Preferred examples of dispersants of the type (b) (ii) include those oligomers having the general H(CH 2 OM.CH 2 OM).PO 3 M 3 , wherein M is a cationic species such that the oligomer is soluble in water and n is a number greater than 1.
  • a preferred example of a dispersant of the type (b)(iii) is a homopolymer of acrylic acid, especially a homopolymer having a molecular weight in the range 2000 to 5000.
  • Preferred examples of dispersants of the type b(iv) include sodium tripolyphosphate.
  • the present invention provides a method of treating an inorganic slurry to maintain the slurry in a substantially homogeneous phase, the method comprising the addition to the slurry of an effective amount of a composition according to the first aspect of the present invention.
  • the inorganic slurry may, for example, comprise a calcium carbonate-based slurry.
  • the inorganic slurry may comprise a pigment slurry, a clay slurry or a cement slurry.
  • the ratio of THP + salt to dispersant in the composition is about 2:1 (as active ingredients).
  • the composition may be added to the slurry in an amount in the range 10 ppm to 1000 ppm (by weight of the slurry), for example about 750 ppm (by weight of the slurry).

Abstract

This invention relates to a composition for treating inorganic slurries and to a method of treating inorganic slurries with the aforesaid composition so as to maintain the slurries in a substantially homogeneous phase. The composition comprises a THP+ salt and a dispersant selected from the group consisting of: (i) phosphonated compound containing at least one tertiary nitrogen atom; (ii) phosphonated oligomers of unsaturated acids; (iii) homopolymers of unsaturated acids; and (iv) Polyphosphates The THP+ salt is preferably THPS

Description

  • This invention relates to a composition for treating inorganic slurries and to a method of treating inorganic slurries with the aforesaid composition so as to maintain the slurries in a substantially homogeneous phase.
  • The present invention will be described herein with particular reference to calcium carbonate-based slurries, especially those used in paper-making processes, although it is not to be construed as being limited thereto.
  • Most inorganic slurries contain about 70% to 80% by weight of solids. Many inorganic slurries (particularly those based on calcium carbonate) are known to be susceptible to bacterial contamination and it has been the practice to add one or more biocidally-active materials to the slurries in order to minimise such contamination.
  • Phosphorus-containing compounds, in particular tetrakis(hydroxyorgano)phosphonium salts (THP+ salts) are known to be effective biocides. Experimental work carried out by the applicants has shown, for example, that the addition of a solution of tetrakis(hydroxymethyl)phosphonium sulphate (THPS) to a calcium carbonate-based slurry can give rise to a reduction in bacterial count of 104 in 2 hours.
  • However, it is also known that addition of THPS alone to a slurry results in instantaneous heterogeneous thickening and aggregation of the slurry.
  • The applicants have found that the use of a composition comprising a THP+ salt and a dispersant will provide continuing preservation against bacterial contamination, while at the same time maintaining the slurry in a substantially homogeneous phase.
  • Accordingly, in a first aspect, the present invention provides a composition for treating an inorganic slurry, the composition comprising:
    • (a) a tetrakis(hydroxyorgano)phosphonium salt (hereinafter THP+ salt); and
    • (b) a dispersant selected from the group consisting of:
      • (i) phosphonated compounds containing at least one tertiary nitrogen atom;
      • (ii) phosphonated oligomers of unsaturated acids;
      • (iii) homopolymers of unsaturated acids;
    • and (iv) polyphosphates.
  • In accordance with the present invention, the THP+ salt is preferably tetrakis(hydroxymethyl)phosphonium sulphate.
  • Alternatively, the THP+ salt may be tetrakis(hydroxymethyl)phosphonium chloride, phosphate, nitrate or oxalate.
  • A preferred example of a dispersant of the type (b)(i) is a compound having one tertiary nitrogen atom, such as a sodium salt of nitrilo-tris(methylene phosphate), particularly the tetra-sodium salt.
  • Preferred examples of dispersants of the type (b) (ii) include those oligomers having the general H(CH2OM.CH2OM).PO3M3, wherein M is a cationic species such that the oligomer is soluble in water and n is a number greater than 1.
  • Other suitable oligomers are disclosed in the applicant's European Patent Specification 0 491 391.
  • A preferred example of a dispersant of the type (b)(iii) is a homopolymer of acrylic acid, especially a homopolymer having a molecular weight in the range 2000 to 5000.
  • Preferred examples of dispersants of the type b(iv) include sodium tripolyphosphate.
  • In a second aspect, the present invention provides a method of treating an inorganic slurry to maintain the slurry in a substantially homogeneous phase, the method comprising the addition to the slurry of an effective amount of a composition according to the first aspect of the present invention.
  • The inorganic slurry may, for example, comprise a calcium carbonate-based slurry.
  • Alternatively, the inorganic slurry may comprise a pigment slurry, a clay slurry or a cement slurry.
  • Preferably, the ratio of THP+ salt to dispersant in the composition is about 2:1 (as active ingredients).
  • Suitably, the composition may be added to the slurry in an amount in the range 10 ppm to 1000 ppm (by weight of the slurry), for example about 750 ppm (by weight of the slurry).
  • The present invention will be illustrated by way of the following examples.
  • In the examples, a 75% calcium carbonate slurry (commercially known as Setacarb) was treated with:
  • EXAMPLE 1 THP+ Salt Alone EXAMPLE 2 THP+ Salt and Dispersant of Type (b)(i). EXAMPLE 3 THP+ Salt and Dispersant of Type (b)(ii).
  • The amounts of each additive used, and the results, are given in the TABLE below.
    TABLE
    Example THP+ salt Dispersant
    No. (ppm) (ppm) Result
    1 (a) THPS (b) (nil) Instant heterogeneous
    750 ppm thickening
    2 (a) THPS b(i) No thickening
    750 ppm 375 ppm
    3 (a) THPS b(ii) No thickening
    750 ppm 375 ppm
  • Notes to TABLE
      • (a) An aqueous solution of tetrakis(hydroxymethyl)phosphonium sulphate (75% a.i.), available as TOLCIDE®-PS75.
      • (b) (i) An aqueous solution of the tetra sodium salt of nitrilo-tris(methylene phosphonic acid), available as BRIQUEST® 301-32S.
      • (b)(ii) A homopolymer of polyacrylic acid, having a molecular weight in the range 2000-5000 and available as BEVALOID®211.

Claims (20)

1-19. (canceled)
20. A method for treating an inorganic slurry to maintain the slurry in a substantially homogeneous phase and to preserve the slurry against bacterial contamination, which comprises the addition to the slurry of an effective amount of a composition comprising:
(a) a tetrakis(hydroxyorgano)phosphonium salt (herein THP+ salt) selected from tetrakis(hydroxymethyl)phosphonium sulphate, tetrakis(hydroxymethyl)phosphonium chloride, tetrakis(hydroxymethyl)phosphonium phosphate, tetrakis(hydroxymethyl)phosphonium nitrate and tetrakis(hydroxymethyl)phosphonium oxalate; and
(b) a dispersant selected from the group consisting of:
(i) phosphonated compounds containing at least one tertiary nitrogen atom; and
(ii) homopolymers of unsaturated acids.
21. A method according to claim 20, in which the THP+ salt is tetrakis(hydroxymethyl)phosphonium sulphate.
22. A method according to claim 20, in which the THP+ salt is tetrakis(hydroxymethyl)phosphonium chloride, phosphate, nitrate or oxalate.
23. A method according to claim 20, in which the dispersant (b(i)) is a phosphonated compound containing one tertiary nitrogen atom.
24. A method according to claim 4, in which the dispersant (b(i)) is a sodium salt of nitrilo-tris(methylene phosphonate).
25. A method according to claim 5, in which the salt is the tetra-sodium salt.
26. A method according to claim 20, in which the dispersant (b(ii)) is a homopolymer of acrylic acid.
27. A method according to claim 26, in which the homopolymer has a molecular weight in the range 2000 to 5000.
28. A method according to claim 20, in which the ratio of THP+ salt to dispersant in the composition is about 2:1 (as active ingredients).
29. A method according to claim 20, in which the composition is added to the slurry in an amount in the range 10 ppm to 1000 ppm (by weight of the slurry).
30. A method according to claim 20, in which the composition is added to the slurry in an amount of about 750 ppm (by weight of the slurry).
31. A method, according to claim 20, in which the slurry comprises a calcium carbonate-based slurry.
32. A method according to claim 20, in which the slurry comprises a pigment slurry, a clay slurry or a cement slurry.
33. A composition for treating an inorganic slurry, the composition comprising:
(a) tetrakis(hydroxyorgano)phosphonium salt (herein THP+ salt) selected from tetrakis(hydroxymethyl)phosphonium sulphate, tetrakis(hydroxymethyl)phosphonium chloride, tetrakis(hydroxymethyl)phosphonium phosphate, tetrakis(hydroxymethyl)phosphonium nitrate and tetrakis(hydroxymethyl)phosphonium oxalate; and
(b) a dispersant which is the tetra sodium salt of nitrilo-tris (methylene phosphonate).
34. A composition according to claim 33, wherein the THP+ salt is tetrakis(hydroxymethyl)phosphonium sulphate.
35. A method of treating an inorganic slurry to maintain the slurry in a substantially homogeneous phase and to preserve the slurry against bacterial contamination, comprising the addition to the slurry of an effective amount of a composition according to claim 33.
36. A composition for treating an inorganic slurry, the composition comprising:
(a) a tetrakis(hydroxymethyl)phosphonium salt (herein THP+ salt) selected from tetrakis(hydroxymethyl)phosphonium sulphate, tetrakis (hydroxymethyl)phosphonium chloride, tetrakis(hydroxymethyl)phosphonium phosphate, tetrakis(hydroxymethyl)phosphonium nitrate and tetrakis(hydroxymethyl)phosphonium oxalate; and
(b) a dispersant which is a homopolymer of acrylic acid, the homopolymer having a molecular weight in the range of 2,000 to 5,000.
37. A composition according to claim 36, wherein the THP+ salt is tetrakis(hydroxymethyl)phosphonium sulphate.
38. A method of treating an inorganic slurry to maintain the slurry in a substantially homogeneous phase and to preserve the slurry against bacterial contamination, comprising the addition to the slurry of an effective amount of a composition according to claim 36.
US10/542,432 2003-01-29 2004-01-12 Treating slurries Abandoned US20060102563A1 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US13/586,012 US20120309718A1 (en) 2003-01-29 2012-08-15 Methods for treating an inorganic slurry
US13/856,058 US8772356B2 (en) 2003-01-29 2013-04-03 Methods for treating an inorganic slurry
US14/285,973 US20140256686A1 (en) 2003-01-29 2014-05-23 Composition for treating an inorganic slurry
US15/412,800 US20170127681A1 (en) 2003-01-29 2017-01-23 Composition for treating an inorganic slurry

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
GB0301975A GB0301975D0 (en) 2003-01-29 2003-01-29 Treating slurries
GB03019759 2003-01-29
PCT/GB2004/000056 WO2004066731A1 (en) 2003-01-29 2004-01-12 Treating slurries

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2004/000056 A-371-Of-International WO2004066731A1 (en) 2003-01-29 2004-01-12 Treating slurries

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US13/586,012 Continuation US20120309718A1 (en) 2003-01-29 2012-08-15 Methods for treating an inorganic slurry

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US20060102563A1 true US20060102563A1 (en) 2006-05-18

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Application Number Title Priority Date Filing Date
US10/542,432 Abandoned US20060102563A1 (en) 2003-01-29 2004-01-12 Treating slurries
US13/586,012 Abandoned US20120309718A1 (en) 2003-01-29 2012-08-15 Methods for treating an inorganic slurry
US13/856,058 Expired - Fee Related US8772356B2 (en) 2003-01-29 2013-04-03 Methods for treating an inorganic slurry
US14/285,973 Abandoned US20140256686A1 (en) 2003-01-29 2014-05-23 Composition for treating an inorganic slurry
US15/412,800 Abandoned US20170127681A1 (en) 2003-01-29 2017-01-23 Composition for treating an inorganic slurry

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Application Number Title Priority Date Filing Date
US13/586,012 Abandoned US20120309718A1 (en) 2003-01-29 2012-08-15 Methods for treating an inorganic slurry
US13/856,058 Expired - Fee Related US8772356B2 (en) 2003-01-29 2013-04-03 Methods for treating an inorganic slurry
US14/285,973 Abandoned US20140256686A1 (en) 2003-01-29 2014-05-23 Composition for treating an inorganic slurry
US15/412,800 Abandoned US20170127681A1 (en) 2003-01-29 2017-01-23 Composition for treating an inorganic slurry

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US (5) US20060102563A1 (en)
EP (1) EP1592303B1 (en)
JP (1) JP4568269B2 (en)
KR (1) KR101076579B1 (en)
CN (2) CN1744820B (en)
AT (1) ATE430476T1 (en)
CA (1) CA2514400C (en)
DE (1) DE602004020971D1 (en)
DK (1) DK1592303T3 (en)
ES (1) ES2324711T3 (en)
GB (1) GB0301975D0 (en)
TW (1) TWI334855B (en)
WO (1) WO2004066731A1 (en)
ZA (1) ZA200505601B (en)

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CA3058628A1 (en) * 2017-03-31 2018-10-04 Dow Global Technologies Llc Microbicidal composition
CN111848015A (en) * 2020-07-21 2020-10-30 蚌埠龙淮建筑科技有限公司 Method for preparing foaming wall material by using municipal sludge

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US3336221A (en) * 1964-11-05 1967-08-15 Calgon Corp Method of inhibiting precipitation and scale formation
US3597251A (en) * 1968-11-19 1971-08-03 Wyandotte Chemical Corp Calcium carbonate product
US3832302A (en) * 1972-01-17 1974-08-27 Halliburton Co Methods for inhibiting scale formation
US3945843A (en) * 1974-07-22 1976-03-23 Nalco Chemical Company Acrylic acid copolymer as pigment dispersant
US4874526A (en) * 1981-05-30 1989-10-17 Ciba-Geigy Corporation Treatment of water
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KR20050114610A (en) 2005-12-06
CN1744820B (en) 2011-10-05
US20130225534A1 (en) 2013-08-29
WO2004066731A1 (en) 2004-08-12
ATE430476T1 (en) 2009-05-15
CN101851439A (en) 2010-10-06
DE602004020971D1 (en) 2009-06-18
US8772356B2 (en) 2014-07-08
US20170127681A1 (en) 2017-05-11
CN1744820A (en) 2006-03-08
GB0301975D0 (en) 2003-02-26
CA2514400C (en) 2012-11-06
CA2514400A1 (en) 2004-08-12
ZA200505601B (en) 2006-04-26
US20120309718A1 (en) 2012-12-06
JP4568269B2 (en) 2010-10-27
US20140256686A1 (en) 2014-09-11
KR101076579B1 (en) 2011-10-24
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