US20170127681A1 - Composition for treating an inorganic slurry - Google Patents

Composition for treating an inorganic slurry Download PDF

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Publication number
US20170127681A1
US20170127681A1 US15/412,800 US201715412800A US2017127681A1 US 20170127681 A1 US20170127681 A1 US 20170127681A1 US 201715412800 A US201715412800 A US 201715412800A US 2017127681 A1 US2017127681 A1 US 2017127681A1
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tetrakis
phosphonium
hydroxymethyl
composition
hydroxyorgano
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US15/412,800
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Christopher Raymond Jones
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Rhodia Operations SAS
Solvay Solutions UK Ltd
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Rhodia Operations SAS
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Priority to US15/412,800 priority Critical patent/US20170127681A1/en
Assigned to RHODIA CONSUMER SPECIALTIES LIMITED reassignment RHODIA CONSUMER SPECIALTIES LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: JONES, CHRISTOPHER
Assigned to RHODIA RECHERCHES ET TECHNOLOGIES reassignment RHODIA RECHERCHES ET TECHNOLOGIES CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: RHODIA UK LIMITED
Assigned to RHODIA OPERATIONS reassignment RHODIA OPERATIONS CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: RHODIA RECHERCHES ET TECHNOLOGIES
Assigned to RHODIA UK LIMITED reassignment RHODIA UK LIMITED CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: RHODIA CONSUMER SPECIALTIES LIMITED
Publication of US20170127681A1 publication Critical patent/US20170127681A1/en
Abandoned legal-status Critical Current

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Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/34—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-halogen bonds; Phosphonium salts
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION 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
    • A01N25/00—Biocides, 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
    • A01N25/02—Biocides, 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
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION 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
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • A01N57/20—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds containing acyclic or cycloaliphatic radicals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B16/00—Use 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT 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
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/02—Compounds of alkaline earth metals or magnesium
    • C09C1/021—Calcium carbonates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT 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
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/42—Clays
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT 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
    • C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
    • C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional 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:
  • THP + salt tetrakis(hydroxyorgano)phosphonium salt
  • 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 a phosphonated oligomer of maleic acid having the general formula H(CHO 2 M.CHO 2 M) n PO 3 M 2 ,
  • 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 1000ppm (by weight of the slurry), for example about 750 ppm (by weight of the slurry).

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Dentistry (AREA)
  • Zoology (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Toxicology (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Paper (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Liquid Crystal Substances (AREA)
  • Threshing Machine Elements (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Treatment Of Sludge (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

A composition for treating an inorganic slurry, the composition including: (a) a tetrakis(hydroxyorgano)phosphonium salt; and (b) a dispersant selected from the group consisting of (i) a phosphonated compound containing at least one tertiary nitrogen atom, the phosphonated compound being a tetra sodium salt of nitrilo-tris(methylene phosphonate); and (ii) a homopolymer of an unsaturated acid, the homopolymer being a homopolymer of acrylic acid having a molecular weight in the range of 2,000 to 5,000.

Description

    CROSS-REFERENCE TO RELATED APPLICATIONS
  • This application is a continuation application of application Ser. No. 14/285,973 filed May 23, 2014, which is a divisional application of application Ser. No.13/856,058 filed Apr. 3, 2013 (U.S. Pat. No. 8,772, 356), which is a continuation application of application Ser. No. 13/586, 012 filed Aug. 15, 2012 (abandoned), which is a continuation application of application Ser. No. 10/542,432 filed Nov. 16, 2005 (abandoned), which is the United States national phase application of International application PCT/GB2004/000056 filed Jan. 12, 2004. The entire contents of each of Ser. Nos. 14/285, 973, 13/856,058, 13/586,012 and 10/542,432, and International application PCT/GB2004/000056 are hereby incorporated by reference herein.
  • 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) 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 a phosphonated oligomer of maleic acid having the general formula H(CHO2M.CHO2M)nPO3M2,
  • 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 1000ppm (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 (15)

1. A composition for treating an inorganic slurry, the composition comprising:
(a) a tetrakis(hydroxyorgano)phosphonium salt; and
(b) a dispersant selected from the group consisting of
(i) a phosphonated compound containing at least one tertiary nitrogen atom, said phosphonated compound being a tetra sodium salt of nitrilo-tris(methylene phosphonate); and
(ii) a homopolymer of an unsaturated acid, said homopolymer being a homopolymer of acrylic acid having a molecular weight in the range of 2,000 to 5,000.
2. The composition according to claim 1, in which the tetrakis(hydroxyorgano)phosphonium salt is tetrakis (hydroxymethyl)phosphonium sulphate.
3. The composition according to claim 1, in which the tetrakis(hydroxyorgano)phosphonium salt is selected from the group consisting of tetrakis(hydroxymethyl)phosphonium chloride, tetrakis(hydroxymethyl)phosphonium phosphate, tetrakis (hydroxymethyl)phosphonium nitrate and tetrakis(hydroxymethyl) phosphonium oxalate.
4. The composition according to claim 1, in which the dispersant is (b(i)).
5. The composition according to claim 1, in which the dispersant is (b(ii)).
6. The composition according to claim 1, in which a ratio of the tetrakis(hydroxyorgano)phosphonium salt to the dispersant, as active ingredients, in the composition is about 2:1.
7. A composition for treating an inorganic slurry, the composition comprising:
(a) a tetrakis(hydroxyorgano)phosphonium salt selected from the group consisting of 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).
8. The composition according to claim 7, in which the tetrakis(hydroxyorgano)phosphonium salt is tetrakis (hydroxymethyl)phosphonium sulphate.
9. The composition according to claim 7, in which the tetrakis(hydroxyorgano)phosphonium salt is selected from the group consisting of tetrakis(hydroxymethyl)phosphonium chloride, tetrakis(hydroxymethyl)phosphonium phosphate, tetrakis (hydroxymethyl)phosphonium nitrate and tetrakis(hydroxymethyl) phosphonium oxalate.
10. The composition according to claim 7, in which a ratio of the tetrakis(hydroxyorgano)phosphonium salt to the dispersant, as active ingredients, in the composition is about 2:1.
11. A composition for treating an inorganic slurry, the composition comprising:
(a) a tetrakis(hydroxyorgano)phosphonium salt selected from the group consisting of 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.
12. The composition according to claim 11, in which the tetrakis(hydroxyorgano)phosphonium salt is tetrakis (hydroxymethyl)phosphonium sulphate.
13. The composition according to claim 11, in which the tetrakis(hydroxyorgano)phosphonium salt is selected from the group consisting of tetrakis(hydroxymethyl)phosphonium chloride, tetrakis(hydroxymethyl)phosphonium phosphate, tetrakis (hydroxymethyl)phosphonium nitrate and tetrakis(hydroxymethyl) phosphonium oxalate.
14. The composition according to claim 11, in which a ratio of the tetrakis(hydroxyorgano)phosphonium salt to the dispersant, as active ingredients, in the composition is about 2:1.
15. A composition for treating an inorganic slurry, the composition comprising:
(a) a tetrakis(hydroxyorgano)phosphonium salt, wherein the tetrakis(hydroxyorgano)phosphonium salt is tetrakis (hydroxymethylphosphonium sulphate; and
(b) a dispersant selected from the group consisting of:
(i) a phosphonated compound containing at least one tertiary nitrogen atom, said compound being a tetra sodium salt of nitrilo-tris(methylene phosphonate); and
(ii) a homopolymer of an unsaturated acid, said homopolymer being a homopolymer of acrylic acid having a molecular weight in the range of 2,000 to 5,000 in which a ratio of the tetrakis(hydroxyorgano)phosphonium salt to the dispersant, as active ingredients, in the composition is about 2:1.
US15/412,800 2003-01-29 2017-01-23 Composition for treating an inorganic slurry Abandoned US20170127681A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US15/412,800 US20170127681A1 (en) 2003-01-29 2017-01-23 Composition for treating an inorganic slurry

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
GB0301975A GB0301975D0 (en) 2003-01-29 2003-01-29 Treating slurries
GB0301975.9 2003-01-29
US10/542,432 US20060102563A1 (en) 2003-01-29 2004-01-12 Treating slurries
PCT/GB2004/000056 WO2004066731A1 (en) 2003-01-29 2004-01-12 Treating slurries
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

Related Parent Applications (1)

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US14/285,973 Continuation US20140256686A1 (en) 2003-01-29 2014-05-23 Composition for treating an inorganic slurry

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US20170127681A1 true US20170127681A1 (en) 2017-05-11

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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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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

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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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CN1744820A (en) 2006-03-08
TWI334855B (en) 2010-12-21
DK1592303T3 (en) 2009-08-17
KR101076579B1 (en) 2011-10-24
CN101851439A (en) 2010-10-06
US20130225534A1 (en) 2013-08-29
CN101851439B (en) 2015-08-19
KR20050114610A (en) 2005-12-06
TW200427637A (en) 2004-12-16
CA2514400C (en) 2012-11-06
EP1592303B1 (en) 2009-05-06
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JP2006521194A (en) 2006-09-21
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US8772356B2 (en) 2014-07-08
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DE602004020971D1 (en) 2009-06-18
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JP4568269B2 (en) 2010-10-27
WO2004066731A1 (en) 2004-08-12

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