US20090186858A1 - Synergistic compositions - Google Patents
Synergistic compositions Download PDFInfo
- Publication number
- US20090186858A1 US20090186858A1 US10/588,474 US58847405A US2009186858A1 US 20090186858 A1 US20090186858 A1 US 20090186858A1 US 58847405 A US58847405 A US 58847405A US 2009186858 A1 US2009186858 A1 US 2009186858A1
- Authority
- US
- United States
- Prior art keywords
- polymer
- copolymer
- unsaturated carboxylic
- carboxylic acid
- biopenetrant
- 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
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- 239000000203 mixture Substances 0.000 title claims abstract description 28
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 64
- 229920001577 copolymer Polymers 0.000 claims abstract description 39
- 241000894006 Bacteria Species 0.000 claims abstract description 14
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000178 monomer Substances 0.000 claims abstract description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-N sulfonic acid Chemical compound OS(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002843 carboxylic acid group Chemical group 0.000 claims abstract description 6
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 claims description 32
- 150000001735 carboxylic acids Chemical class 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- 229920005604 random copolymer Polymers 0.000 claims description 5
- 238000009472 formulation Methods 0.000 claims description 3
- YIEDHPBKGZGLIK-UHFFFAOYSA-L tetrakis(hydroxymethyl)phosphanium;sulfate Chemical group [O-]S([O-])(=O)=O.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO YIEDHPBKGZGLIK-UHFFFAOYSA-L 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 241000195493 Cryptophyta Species 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 2
- 241000233866 Fungi Species 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 238000011109 contamination Methods 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- VMFONZZSAQZUFB-UHFFFAOYSA-N tetrakis(hydroxymethyl)phosphanium phosphite Chemical group [O-]P([O-])[O-].OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO VMFONZZSAQZUFB-UHFFFAOYSA-N 0.000 claims 1
- 230000003115 biocidal effect Effects 0.000 abstract description 5
- 238000004090 dissolution Methods 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 2
- 239000000243 solution Substances 0.000 description 12
- 239000004094 surface-active agent Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 101100288310 Arabidopsis thaliana KTI2 gene Proteins 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- ZNSMNVMLTJELDZ-UHFFFAOYSA-N Bis(2-chloroethyl)ether Chemical compound ClCCOCCCl ZNSMNVMLTJELDZ-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- -1 THP salts Chemical class 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 239000003129 oil well Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910021653 sulphate ion Inorganic materials 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- NFMAZVUSKIJEIH-UHFFFAOYSA-N bis(sulfanylidene)iron Chemical compound S=[Fe]=S NFMAZVUSKIJEIH-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007922 dissolution test Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical class [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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
- A01N57/18—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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B17/00—Methods preventing fouling
-
- 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
- C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
- C11D7/36—Organic compounds containing phosphorus
-
- 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
- C23F11/167—Phosphorus-containing compounds
- C23F11/1676—Phosphonic acids
-
- 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
- C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
- C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
-
- 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
- A01N2300/00—Combinations or mixtures of active ingredients covered by classes A01N27/00 - A01N65/48 with other active or formulation relevant ingredients, e.g. specific carrier materials or surfactants, covered by classes A01N25/00 - A01N65/48
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/04—Surfactants, used as part of a formulation or alone
Definitions
- This invention relates to synergistic biocidal or metal sulphide dissolving compositions.
- the present invention is a selection invention relative to our published P.C.T. application WO 99/33345.
- the said WO 99/33345 discloses synergistic biocidal compositions comprising “THP”, a non-surfactant biopenetrant compatible with “THP” and optionally a surfactant.
- TPP is defined in WO 99/33345 as meaning either a tetrakis(hydroxyalkyl)phosphonium salt or a tris(hydroxyalkyl)phosphine. To avoid confusion we shall hereinafter refer to “THP salts” or “THP” respectively.
- non-surfactant biopenetrants disclosed in the said WO 99/33345 include phosphonated derivatives of carboxylic acids, for example the phosphonated telomers disclosed in our published European applications EP-A-0 491 391 and EP-A-0 861 846.
- non-surfactant biopenetrants disclosed in the said WO 99/33345 include a copolymer of N,N,N′,N′-tetramethyl-1,2-diaminoethane with bis(2-chloroethyl)ether. This is commercially available under the trade name WSCP and will hereinafter be so referred to.
- examples disclosed in the said WO 99/33345 include sulphonated (anionic) surfactants and cationic surfactants such as those based on quaternary ammonium compounds, as well as non-ionic, amphoteric and semi-polar surfactants.
- the biopenetrant is a phosphonic acid-tipped polymer or copolymer, it acts synergistically with a THP salt to considerably enhance the biocidal efficacy of the THP salt against both planktonic (free-swimming) and sessile (attached) bacteria.
- biopenetrant is a phosphonic acid-tipped polymer or copolymer, it acts synergistically with a THP salt to enhance the efficacy of the THP salt in the dissolution of metal sulphide, especially iron sulphide, scale.
- the present invention provides a synergistic composition comprising:
- the synergistic composition may be a synergistic biocidal composition and/or a synergistic metal sulphide (e.g. iron sulphide) dissolving composition.
- a synergistic metal sulphide e.g. iron sulphide
- the THP salt is tetrakis(hydroxymethyl)phosphonium sulphate (THPS).
- THP salts include the phosphite, bromide, fluoride, chloride, phosphate, carbonate, acetate, formate, citrate, borate, and silicate.
- the biopenetrant may comprise a polymer of an unsaturated carboxylic acid or a copolymer of an unsaturated carboxylic acid with a sulphonic acid, said polymer or copolymer being either terminated by vinylphosphonic acid (VPA) or vinylidene-1,1-diphosphonic acid (VDPA) or having such monomers incorporated into the polymer backbone; accordingly the biopenetrant may be a random copolymer incorporating VPA and/or VDPA monomers.
- VPA vinylphosphonic acid
- VDPA vinylidene-1,1-diphosphonic acid
- the polymer or copolymer of the biopenetrant may suitably be a polyacrylate or an acrylate/sulphonate copolymer.
- the biopenetrant may be a polyacrylate terminated with vinylphosphonic acid, (hereinafter “VPA end-capped polymer”) or with vinylidene-1,1-diphosphonic acid (hereinafter “VDPA end-capped polymer”), or may be a polyacrylate incorporating VPA and/or VDPA monomers.
- VPA end-capped polymer vinylphosphonic acid
- VDPA end-capped polymer vinylidene-1,1-diphosphonic acid
- the biopenetrant may be an acrylate/sulphonate copolymer terminated with vinylidene-1,1-diphosphonic acid (hereinafter “VDPA end-capped copolymer”) or with vinylphosphonic acid (hereinafter “VPA end-capped co-polymer”), or may be an acrylate/sulphonate copolymer incorporating VPA and/or VDPA monomers.
- VDPA end-capped copolymer vinylidene-1,1-diphosphonic acid
- VPA end-capped co-polymer vinylphosphonic acid
- the preferred ratio of VPA or VDPA end-capped polymer or copolymer to THP salt is, when expressed as a percentage by weight, in the range of from 0.5 to 50%, such as from 0.5 to 30%; preferably from 1 to 25%, such as from 1 to 20%, for example from 1 to 10% or from 2 to 8%; most preferably from 1 to 5%, for example from 3 to 5% (based upon active solids and upon a 1 to 74%, for example a 50%, active THP salt formulation).
- the biopenetrant is a VPA end-capped polymer or VDPA end-capped copolymer.
- VPA end-capped polymer or VDPA end-capped copolymer to THP salt is, when expressed as a percentage by weight, in the range of from 0.5 to 50%, such as from 0.5 to 30%; preferably from 1 to 25%, such as from 1 to 20%, for example from 1 to 10% or from 2 to 8%; most preferably from 1 to 5%, for example from 3 to 5% (based upon active solids and upon a 1 to 74%, for example a 50%, active THP salt formulation).
- composition may, in one embodiment, be provided in the form of a solution, for example an aqueous solution.
- composition may be supplied as a solid, for example a solid formed by coating the components onto, or absorbing the components into, a powdery granular or porous acid substrate such as adipic acid or by incorporation into a waxy substrate.
- compositions according to the present invention may be used as biocides against both planktonic (free-swimming) and sessile (attached) bacteria.
- compositions according to the present invention are equally effective in reducing the level of general heterotrophic bacteria and of sulphate reducing bacteria in waters.
- the invention therefore also provides a method of treating a water system contaminated, or liable to contamination, with microbes such as bacteria, fungi or algae, which method comprises adding to said system separately or together, a biocidally active amount of a THP salt and a biopenetrant, in which the biopenetrant comprises a polymer of an unsaturated carboxylic acid or a copolymer of an unsaturated carboxylic acid with a sulphonic acid, said polymer or copolymer being terminated by a mono- or di-phosphonated unsaturated carboxylic acid group or being a random copolymer containing a mono or di-phosphonated unsaturated carboxylic acid, thereby killing at least some of said microbes.
- the biopenetrant comprises a polymer of an unsaturated carboxylic acid or a copolymer of an unsaturated carboxylic acid with a sulphonic acid, said polymer or copolymer being terminated by a mono- or di-phosphonated uns
- the water system may, for instance, be contaminated with bacterial slime and/or planktonic bacteria.
- the invention may be of use for treating aerobic systems such as cooling towers, paper processing systems and waste water systems, and also for anaerobic systems, such as oil wells, e.g. during secondary recovery.
- the invention may also be suitable for use in the preservation of slurries and functional fluids, such as drilling muds, completion fluids, stimulation fluids and fracturing fluids.
- compositions according to the present invention may also be used to dissolve metal sulphides, preferably iron sulphide; in particular they may be used to dissolve iron sulphide scale.
- metal sulphide may be lead sulphide or zinc sulphide or a combination of iron or lead and zinc sulphides.
- the iron sulphide may typically be troilite (FeS) or pyrite (FeS 2 ), but any iron sulphide species can be dissolved using the invention.
- the invention therefore also provides a method of treating a water system containing or in contact with a metal sulphide scale, for example an iron sulphide scale, which method comprises adding to said system separately or together, a THP salt and a biopenetrant, in which the biopenetrant comprises a polymer of an unsaturated carboxylic acid or a copolymer of an unsaturated carboxylic acid with a sulphonic acid, said polymer or copolymer being terminated by a mono- or di-phosphonated unsaturated carboxylic acid group or being a random copolymer containing a mono or di-phosphonated unsaturated carboxylic acid, thereby dissolving at least part of said scale.
- a metal sulphide scale for example an iron sulphide scale
- the invention may be of use in the oil and gas industry, for treating systems such as oil wells, gas wells, pipelines, storage vessels and production equipment, e.g. during secondary recovery, and in other industrial water systems,. for instance in paper industry systems.
- Test Product GHB Viable bacteria after 75 ppm ai THPS dosed for 3 hours Test Product GHB SRB Control 1 ⁇ 10 4 1 ⁇ 10 6 Unformulated THPS 1 ⁇ 10 2 1 ⁇ 10 4 THPS/VPA polymer* ⁇ 10 ⁇ 10 THPS/VDPA polymer* 1 ⁇ 10 2 1 ⁇ 10 2 THPS/5% quaternary 1 ⁇ 10 2 1 ⁇ 10 3 ammonium compound(b) *In each case, the ratio of THPS to “polymer” was 50% a.i. THPS to 5% “polymer”, the “polymer” comprising 25% solids as the sodium salt.
- VPA polymer ⁇ VPA polymer solution having 20% active ingredient (20 g)+de-ionised water (80 g)
- VDPA polymer ⁇ VDPA polymer solution having 20% active ingredient (20 g)+de-ionised water (80 g)
- THPS/5% VDPA polymer ⁇ THPS (26.6 g)+VDPA polymer solution having 20% active ingredient (5 g)+de-ionised water (68.4 g)
- the iron concentrations in the filtered solutions were also measured using the iron method on the Hach DR2000 spectrophotometer.
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- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Health & Medical Sciences (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
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Abstract
A synergistic composition comprising a THP salt and a biopenetrant, in which the biopenetrant comprises a polymer of an unsaturated carboxylic acid or a copolymer of an unsaturated carboxylic acid with a sulphonic acid, said polymer or copolymer being terminated by a mono- or diphosphonated unsaturated carboxylic acid group or having such monomers incorporated into the polymer backbone. This composition acts synergistically to enhance the biocidal efficacy of the THP salt against both planktonic (free-swimming) and sessile (attached) bacteria, and also acts synergistically to enhance the efficacy of the THP salt in the dissolution of iron sulphide scale.
Description
- This invention relates to synergistic biocidal or metal sulphide dissolving compositions.
- The present invention is a selection invention relative to our published P.C.T. application WO 99/33345.
- The said WO 99/33345 discloses synergistic biocidal compositions comprising “THP”, a non-surfactant biopenetrant compatible with “THP” and optionally a surfactant.
- The term “THP” is defined in WO 99/33345 as meaning either a tetrakis(hydroxyalkyl)phosphonium salt or a tris(hydroxyalkyl)phosphine. To avoid confusion we shall hereinafter refer to “THP salts” or “THP” respectively.
- Examples of non-surfactant biopenetrants disclosed in the said WO 99/33345 include phosphonated derivatives of carboxylic acids, for example the phosphonated telomers disclosed in our published European applications EP-A-0 491 391 and EP-A-0 861 846.
- Other non-surfactant biopenetrants disclosed in the said WO 99/33345 include a copolymer of N,N,N′,N′-tetramethyl-1,2-diaminoethane with bis(2-chloroethyl)ether. This is commercially available under the trade name WSCP and will hereinafter be so referred to.
- Where surfactants are used, examples disclosed in the said WO 99/33345 include sulphonated (anionic) surfactants and cationic surfactants such as those based on quaternary ammonium compounds, as well as non-ionic, amphoteric and semi-polar surfactants.
- We have now unexpectedly found that where the biopenetrant is a phosphonic acid-tipped polymer or copolymer, it acts synergistically with a THP salt to considerably enhance the biocidal efficacy of the THP salt against both planktonic (free-swimming) and sessile (attached) bacteria.
- It has also unexpectedly been found that where the biopenetrant is a phosphonic acid-tipped polymer or copolymer, it acts synergistically with a THP salt to enhance the efficacy of the THP salt in the dissolution of metal sulphide, especially iron sulphide, scale.
- Accordingly, the present invention provides a synergistic composition comprising:
-
- (i) a THP salt (as hereinbefore defined) and
- (ii) a biopenetrant
in which the biopenetrant comprises a polymer of an unsaturated carboxylic acid or a copolymer of an unsaturated carboxylic acid with a sulphonic acid, said polymer or copolymer being either terminated by a mono-or di-phosphonated unsaturated carboxylic acid or having such monomers incorporated into the polymer backbone.
- The synergistic composition may be a synergistic biocidal composition and/or a synergistic metal sulphide (e.g. iron sulphide) dissolving composition.
- Preferably, the THP salt is tetrakis(hydroxymethyl)phosphonium sulphate (THPS). Other THP salts include the phosphite, bromide, fluoride, chloride, phosphate, carbonate, acetate, formate, citrate, borate, and silicate.
- The biopenetrant may comprise a polymer of an unsaturated carboxylic acid or a copolymer of an unsaturated carboxylic acid with a sulphonic acid, said polymer or copolymer being either terminated by vinylphosphonic acid (VPA) or vinylidene-1,1-diphosphonic acid (VDPA) or having such monomers incorporated into the polymer backbone; accordingly the biopenetrant may be a random copolymer incorporating VPA and/or VDPA monomers.
- The polymer or copolymer of the biopenetrant may suitably be a polyacrylate or an acrylate/sulphonate copolymer.
- In accordance with preferred embodiments of the present invention, the biopenetrant may be a polyacrylate terminated with vinylphosphonic acid, (hereinafter “VPA end-capped polymer”) or with vinylidene-1,1-diphosphonic acid (hereinafter “VDPA end-capped polymer”), or may be a polyacrylate incorporating VPA and/or VDPA monomers.
- In other preferred embodiments, the biopenetrant may be an acrylate/sulphonate copolymer terminated with vinylidene-1,1-diphosphonic acid (hereinafter “VDPA end-capped copolymer”) or with vinylphosphonic acid (hereinafter “VPA end-capped co-polymer”), or may be an acrylate/sulphonate copolymer incorporating VPA and/or VDPA monomers.
- In the composition of the present invention, the preferred ratio of VPA or VDPA end-capped polymer or copolymer to THP salt, is, when expressed as a percentage by weight, in the range of from 0.5 to 50%, such as from 0.5 to 30%; preferably from 1 to 25%, such as from 1 to 20%, for example from 1 to 10% or from 2 to 8%; most preferably from 1 to 5%, for example from 3 to 5% (based upon active solids and upon a 1 to 74%, for example a 50%, active THP salt formulation).
- In one embodiment, the biopenetrant is a VPA end-capped polymer or VDPA end-capped copolymer.
- The preferred ratio of VPA end-capped polymer or VDPA end-capped copolymer to THP salt is, when expressed as a percentage by weight, in the range of from 0.5 to 50%, such as from 0.5 to 30%; preferably from 1 to 25%, such as from 1 to 20%, for example from 1 to 10% or from 2 to 8%; most preferably from 1 to 5%, for example from 3 to 5% (based upon active solids and upon a 1 to 74%, for example a 50%, active THP salt formulation).
- The composition may, in one embodiment, be provided in the form of a solution, for example an aqueous solution.
- Alternatively the composition may be supplied as a solid, for example a solid formed by coating the components onto, or absorbing the components into, a powdery granular or porous acid substrate such as adipic acid or by incorporation into a waxy substrate.
- As noted above, the compositions according to the present invention may be used as biocides against both planktonic (free-swimming) and sessile (attached) bacteria.
- We have found that the compositions according to the present invention are equally effective in reducing the level of general heterotrophic bacteria and of sulphate reducing bacteria in waters.
- The invention therefore also provides a method of treating a water system contaminated, or liable to contamination, with microbes such as bacteria, fungi or algae, which method comprises adding to said system separately or together, a biocidally active amount of a THP salt and a biopenetrant, in which the biopenetrant comprises a polymer of an unsaturated carboxylic acid or a copolymer of an unsaturated carboxylic acid with a sulphonic acid, said polymer or copolymer being terminated by a mono- or di-phosphonated unsaturated carboxylic acid group or being a random copolymer containing a mono or di-phosphonated unsaturated carboxylic acid, thereby killing at least some of said microbes.
- The water system may, for instance, be contaminated with bacterial slime and/or planktonic bacteria. The invention may be of use for treating aerobic systems such as cooling towers, paper processing systems and waste water systems, and also for anaerobic systems, such as oil wells, e.g. during secondary recovery. The invention may also be suitable for use in the preservation of slurries and functional fluids, such as drilling muds, completion fluids, stimulation fluids and fracturing fluids.
- As mentioned above, the compositions according to the present invention may also be used to dissolve metal sulphides, preferably iron sulphide; in particular they may be used to dissolve iron sulphide scale. However, the metal sulphide may be lead sulphide or zinc sulphide or a combination of iron or lead and zinc sulphides.
- The iron sulphide may typically be troilite (FeS) or pyrite (FeS2), but any iron sulphide species can be dissolved using the invention.
- The invention therefore also provides a method of treating a water system containing or in contact with a metal sulphide scale, for example an iron sulphide scale, which method comprises adding to said system separately or together, a THP salt and a biopenetrant, in which the biopenetrant comprises a polymer of an unsaturated carboxylic acid or a copolymer of an unsaturated carboxylic acid with a sulphonic acid, said polymer or copolymer being terminated by a mono- or di-phosphonated unsaturated carboxylic acid group or being a random copolymer containing a mono or di-phosphonated unsaturated carboxylic acid, thereby dissolving at least part of said scale.
- The invention may be of use in the oil and gas industry, for treating systems such as oil wells, gas wells, pipelines, storage vessels and production equipment, e.g. during secondary recovery, and in other industrial water systems,. for instance in paper industry systems.
- The present invention will be illustrated by way of the following examples.
- In the examples, the various abbreviations have the following meaning:
-
- VPA polymer: a vinylphosphonic acid-terminated polyacrylate of molecular weight about 4000
- VDPA copolymer: a vinylidene-diphosphonic acid-terminated acrylate/sulphonate copolymer of molecular weight 5000-6000
- GHB: general heterotrophic bacteria
- SRB: sulphate reducing bacteria
- WHO water: World Health Organisation Standard Hardness Water (see TABLE I below)
- SMOW water: Standard Mean Ocean Water. (see TABLE II below)
- THPS: a 50% aqueous solution of tetrakis (hydroxymethyl) phosphonium sulphate
- WSCP: copolymer of N,N,N′,N′-tetramethyl-1,2-diamino ethane and bis(2-chloroethyl)ether.
-
TABLE I WHO Standard Hardness Water 1 litre contains: CaCl2 (anhydrous) 0.305 g MgCl2•6H2O 0.139 g -
TABLE II Standard Mean Ocean Water 5 litres contain: NaCl 122.65 g MgCl2•6H2O 55.52 g Na2SO4 20.45 g CaCl2•2H2O 7.69 g KCl 3.48 g NaHCO3 1.00 g KBr 0.50 g pH adjusted to 8.2 by means of 0.1N NaOH -
-
Log Reduction of General Heterotrophic Bacteria (based upon 50 ppm ai THPS) Contact period Test Product 1 hour contact 3 hour contact Control 0 0 Unformulated THPS 1 5.8 THPS/VPA polymer* 7.4 Total kill THPS/VDPA polymer* 7.4 Total kill THPS/0.7% WSCP 3.7 7.4 -
-
Log reduction values for 75 ppm ai THPS/3 hour contact Test Product GHB SRB Control 0 0 Unformulated THPS 3.8 3 THPS/VPA polymer* 5.1 3 -
-
Viable bacteria (GHB) after 75 ppm ai THPS dosed for 3 hours Test Product Control 1 × 105 Unformulated THPS 1 × 105 THPS/VPA polymer* 1 × 102 THPS/VDPA polymer* <10 THPS/2% sulphonated 1 × 103 surfactant (a) -
-
Viable bacteria after 75 ppm ai THPS dosed for 3 hours Test Product GHB SRB Control 1 × 104 1 × 106 Unformulated THPS 1 × 102 1 × 104 THPS/VPA polymer* <10 <10 THPS/VDPA polymer* 1 × 102 1 × 102 THPS/5% quaternary 1 × 102 1 × 103 ammonium compound(b) *In each case, the ratio of THPS to “polymer” was 50% a.i. THPS to 5% “polymer”, the “polymer” comprising 25% solids as the sodium salt. - (a) A di-sodium salt of a mixed mono- and di-alkyl disulphonated diphenyl oxide, available as DOWFAX® 2A1.
- (b) An alkyl dimethyl benzyl ammonium chloride, available as EMPIGEN®BAC 50.
- The following solutions were made:
- (a) THPS: −THPS (26.6 g)+de-ionised water (73.4 g)
- (b) VPA polymer: −VPA polymer solution having 20% active ingredient (20 g)+de-ionised water (80 g)
- (c) VDPA polymer: −VDPA polymer solution having 20% active ingredient (20 g)+de-ionised water (80 g)
- (d) THPS/5% VPA polymer: −THPS (26.6 g)+VPA polymer solution having 20% active ingredient (5 g)+de-ionised water (68.4 g).
- (e) THPS/5% VDPA polymer: −THPS (26.6 g)+VDPA polymer solution having 20% active ingredient (5 g)+de-ionised water (68.4 g)
- (f) THPS/20% VPA polymer: −THPS (26.6 g)+VPA polymer solution having 20% active ingredient (20 g)+de-ionised water (53.4 g)
- (g) THPS/20% VDPA polymer: −THPS (26.6 g)+VDPA polymer solution having 20% active ingredient (20 g)+de-ionised water (53.4 g)
- To each of these solutions was added 2 g (accurately weighed) of an iron sulphide field scale (from a water injection system). The solutions were then stirred in a heated water bath for 20 hrs at 50° C., after this time they were filtered through a weighed filter paper. The filter paper and solids were then allowed to dry before re-weighing; the weight of solids remaining was therefore determined, and the % weight loss calculated.
- The iron concentrations in the filtered solutions were also measured using the iron method on the Hach DR2000 spectrophotometer.
-
Fe2+ concentration Dissolver pH % wt loss in solution ppm (a)THPS 3.23 63 3120 (b)VPA polymer 4.54 60 1310 (c)VDPA polymer 3.28 47 1430 (d)THPS + 5% VPA 3.77 74 3320 polymer (e)THPS + 5% VDPA 3.13 78 3560 polymer (f)THPS + 20% VPA 3.94 76 3480 polymer (g)THPS + 20% VDPA 2.99 83 5260 polymer
Claims (14)
1-20. (canceled)
21. A synergistic composition comprising: (i) a THP salt and (ii) a biopenetrant, wherein the biopenetrant comprises a polymer of an unsaturated carboxylic acid or a copolymer of an unsaturated carboxylic acid with a sulphonic acid, said polymer or copolymer being terminated by a mono- or di-phosphonated unsaturated carboxylic acid group or having such monomers incorporated into the polymer backbone.
22. A composition according to claim 21 , wherein the THP salt is tetrakis(hydroxymethyl) phosphonium sulphate.
23. A composition according to claim 21 , wherein the THP salt is tetrakis (hydroxymethyl) phosphonium phosphite, bromide, fluoride, chloride, phosphate, carbonate, acetate, formats, citrate, borate or silicate.
24. A composition according to claim 21 , wherein the biopenetrant comprises a polymer of an unsaturated carboxylic acid or a copolymer of an unsaturated carboxylic acid with a sulphonic acid, said polymer or copolymer being either terminated by vinylphosphonic acid (VPA) or vinylidene-1,1-diphosphonic acid (VDPA) or having such monomers incorporated into the polymer backbone.
25. A composition according to claim 21 , wherein the polymer or copolymer of the biopenetrant is a polyacrylate or an acrylate/sulphonate copolymer.
26. A composition according to claim 25 , wherein the biopenetrant is a VPA end-capped polymer or a VDPA end-capped polymer or a polyacrylate incorporating VPA and/or VDPA monomers.
27. A composition according to claim 25 , wherein the biopenetrant is a VDPA end-capped copolymer or a VPA end-capped copolymer (both as hereinbefore defined) or an acrylate/sulphonate copolymer incorporating VPA and/or VDPA monomers.
28. A composition according to claim 26 , wherein the proportion of VPA or VDPA polymer or copolymer is in the range of from 1 to 50% by weight, based upon active solids and a 1 to 74% THP salt formulation.
29. A composition according to claim 28 , wherein the proportion is in the range of from 1 to 25% by weight.
30. A composition according to claim 9, wherein the proportion is in the range of from 1 to 5% by weight.
31. A method of treating a water system contaminated, or liable to contamination, with microbes such as bacteria, fungi or algae, comprising the steps of:
a) adding to said system separately or together, a biocidally active amount of a THP salt and a biopenetrant, wherein the biopenetrant comprises a polymer of an unsaturated carboxylic acid or a copolymer of an unsaturated carboxylic acid with a sulphonic acid, said polymer or copolymer being terminated by a mono- or di-phosphonated unsaturated carboxylic acid group or being a random copolymer containing a mono or di-phosphonated unsaturated carboxylic acid, thereby killing at least some of said microbes.
32. A method of treating a water system containing or in contact with an metal sulphide scale, comprising the step of:
a) adding to said system separately or together, a THP salt and a biopenetrant, wherein the biopenetrant comprises a polymer of an unsaturated carboxylic acid or a copolymer of an unsaturated carboxylic acid with a sulphonic acid, said polymer or copolymer being terminated by a mono- or di-phosphonated unsaturated carboxylic acid group or being a random copolymer containing a mono or di-phosphonated unsaturated carboxylic acid, and
b) thereby dissolving at least part of said scale.
33. The method of claim 32 wherein the scale is iron sulphide scale.
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GBGB0402395.8A GB0402395D0 (en) | 2004-02-03 | 2004-02-03 | Synergistic biocidal compositions |
GB0402395.8 | 2004-02-03 | ||
PCT/GB2005/000373 WO2005074688A2 (en) | 2004-02-03 | 2005-02-03 | Synergistic biocidal compositions comprising a thp salt |
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US14/604,423 Abandoned US20150141377A1 (en) | 2004-02-03 | 2015-01-23 | Synergistic composition |
US15/807,315 Active US10178867B2 (en) | 2004-02-03 | 2017-11-08 | Treating microbe contamination in water with THP salts and polymeric biopenetrants |
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US15/807,315 Active US10178867B2 (en) | 2004-02-03 | 2017-11-08 | Treating microbe contamination in water with THP salts and polymeric biopenetrants |
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US20100047353A1 (en) * | 2007-03-21 | 2010-02-25 | Ashish Batra | Hair care composition |
US20180044571A1 (en) * | 2016-08-10 | 2018-02-15 | Rhodia Operations | Combined uses of a phosphorous compound for iron sulphide dissolution and bacterial control |
US20180105732A1 (en) * | 2015-04-02 | 2018-04-19 | Clariant International, Ltd. | Composition And Method For Inhibition Of Sulfide Scales |
EP3711486A1 (en) | 2019-03-19 | 2020-09-23 | Rhodia Operations | Biocidal compositions including a phosphonium quaternary cationic surfactant and methods for using same |
EP3711485A1 (en) | 2019-03-19 | 2020-09-23 | Rhodia Operations | Synergistic biocidal compositions and methods for using same |
US20210395123A1 (en) * | 2018-09-28 | 2021-12-23 | Rhodia Operations | Treatment of iron sulphide deposits |
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DK2175721T3 (en) | 2007-07-24 | 2017-05-01 | Dow Global Technologies Llc | Methods and Formulations for Reducing and Inhibiting the Growth of Microbes Concentration in Water-Based Fluids and Systems Used With These |
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CN101348298B (en) * | 2008-09-02 | 2010-06-23 | 金堆城钼业股份有限公司 | Rapid method for removing chromium in waste water |
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AU2010298611B2 (en) * | 2009-09-25 | 2013-10-31 | Dow Global Technologies Inc. | Synergistic antimicrobial composition |
GB2488768A (en) * | 2011-03-07 | 2012-09-12 | Rhodia Operations | Treatment of hydrocarbon-containing systems |
JP6031522B2 (en) | 2011-09-15 | 2016-11-24 | ダウ グローバル テクノロジーズ エルエルシー | Biocide compositions and methods of use |
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AU667295B2 (en) * | 1990-12-18 | 1996-03-21 | Albright & Wilson Uk Limited | Water treatment agent |
GB9703951D0 (en) * | 1997-02-26 | 1997-04-16 | Albright & Wilson Uk Ltd | Novel phosphino derivatives |
GB9725828D0 (en) * | 1997-12-06 | 1998-02-04 | Albright & Wilson Uk Ltd | Fabric treatment and polymeric compositions therefor |
AU736266B2 (en) | 1997-12-23 | 2001-07-26 | Rhodia Consumer Specialties Limited | Biocidal compositions and treatments |
AU6217499A (en) * | 1998-10-14 | 2000-05-01 | Albright & Wilson Uk Limited | Leaching divalent metal salts |
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US20100047353A1 (en) * | 2007-03-21 | 2010-02-25 | Ashish Batra | Hair care composition |
US20180105732A1 (en) * | 2015-04-02 | 2018-04-19 | Clariant International, Ltd. | Composition And Method For Inhibition Of Sulfide Scales |
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US20210395123A1 (en) * | 2018-09-28 | 2021-12-23 | Rhodia Operations | Treatment of iron sulphide deposits |
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WO2020191160A1 (en) * | 2019-03-19 | 2020-09-24 | Rhodia Operations | Biocidal compositions including a phosphonium quaternary cationic surfactant and methods for using same |
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CN1980575B (en) | 2011-04-06 |
BRPI0506545B1 (en) | 2015-09-29 |
EG24855A (en) | 2010-10-27 |
US20150141377A1 (en) | 2015-05-21 |
DK1744630T3 (en) | 2015-08-24 |
AR055808A1 (en) | 2007-09-12 |
US20180064112A1 (en) | 2018-03-08 |
NO338973B1 (en) | 2016-11-07 |
MXPA06008792A (en) | 2007-04-13 |
WO2005074688A2 (en) | 2005-08-18 |
EP1744630B1 (en) | 2015-05-20 |
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