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
  • A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
• • 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
• • 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
  • 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
• • 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
• • 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
  • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
  • C02F2103/10—Nature of the water, waste water, sewage or sludge to be treated from quarries or from mining activities
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2303/00—Specific treatment goals
  • C02F2303/08—Corrosion inhibition
• • C—CHEMISTRY; METALLURGY
  • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
  • C02F2303/00—Specific treatment goals
  • C02F2303/20—Prevention of biofouling

Definitions

• the present invention relates to a method for suppressing or mitigating the problems associated with corrosion and new formulations for use in such a process.
• THP + salts tetrakis (hydroxyorgano) phosphonium
• THPS tetrakis (hydroxymethyl) phosphonium sulfate
• THP + salts can cause corrosion problems, particularly corrosion of ferrous surfaces, when used in aqueous systems at high concentrations.
• THPS tetrachlorosulfate
• an ammonium salt to improve performance.
• this combination of THPS and an ammonium salt added at the high temperatures that can be encountered in oilfield applications, can be corrosive, for example for mild steel and other components. metal.
• WO 2005/040050 formulations comprising a THP + salt and a primary, secondary or tertiary alcohol having an acetylenic bond in the carbon skeleton have been described to be used in order to avoid this problem, by allowing inhibition at both metal sulphide deposition and corrosion.
• WO 2004/083131 also discloses formulations for use in the treatment of corrosion and deposition of metal sulfides in aqueous systems, which formulations comprise a THP + salt and a thio-substituted compound.
• alkylphosphonic acid reduces or prevents the corrosive effect of a THP + salt.
• the Alkylphosphonic acids are not specialized acidic inhibitors, and therefore this effect would not have been anticipated.
• the invention thus proposes, in a first aspect, a formulation for the treatment of aqueous systems comprising a THP + salt (as defined above) and an alkylphosphonic acid.
• THP + salt acts conventionally, e.g. as a biocide or to dissolve / disperse a metal sulfide, while alkylphosphonic acid controls the corrosive effect of the THP + salt.
• Such formulations are also beneficial because the presence of alkylphosphonic acid surprisingly increases the effectiveness of the THP + salt as a biocide.
• alkyl phosphonic acid is an acid (alkyl to C 30) phosphonic acid, preferably an acid (C 2 -C 2 5) phosphonic acid, more preferably an acid (alkyl C 3 -C 2 o) phosphonic acid, most preferably an acid (C 5 to C 5) phosphonic acid, for example an acid (alkyl Ce to Ci 2) phosphonic acid, such as an acid (C 7, Cg, C9, or Cio) phosphonic acid.
• the alkyl group may be an unsubstituted or substituted alkyl group.
• the alkyl group is substituted, one or more, for example two or more, such as three or more, hydrogens of the alkyl moiety are substituted with a functional group.
• the substituent groups may be the same or different.
• the substituent functional group may be any suitable group but may be, for example, a halogeno group (e.g., fluoro, chloro or bromo).
• the alkyl group may be a straight or branched chain.
• alkylphosphonic acid examples include octylphosphonic acid, nonylphosphonic acid, decylphosphonic acid and dodecylphosphonic acid.
• the alkylphosphonic acid is octylphosphonic acid.
• the anion of the THP + salt must be compatible with the aqueous system.
• the anion must render the THP + salt water soluble.
• Preferred anions for the THP + salt include sulfate, chloride, phosphate, bromide, fluoride, carbonate, citrate, lactate, tartrate, borate, silicate, formate and acetate. Sulphate is particularly preferred.
• the ratio of THP + to alkylphosphonic acid in the formulation is typically in the range of from 1: 1 to 750: 1, preferably from 10: 1 to 500: 1, more preferably from 15: 1 to 300: 1, such as From 20: 1 to 100: 1, for example from 25: 1 to 75: 1, most preferably from 30: 1 to 60: 1, for example from 35: 1 to 55: 1, as from 40: 1 to 50: 1.
• the formulation may include a surfactant.
• the surfactant is preferably a cationic surfactant, for example a quaternary ammonium compound, an N-alkylated heterocyclic compound or a quaternized amido-amine.
• anionic, amphoteric or nonionic surfactants can be used.
• Aminomethane phosphonates can replace ammonium salts in the aqueous system.
• the formulation may include a solvent.
• the solvent may be aqueous or organic.
• solvents examples include water, dimethylsulfoxide (DMSO), alkylene glycols, glycol ethers and tetrahydrofuran (THF).
• DMSO dimethylsulfoxide
• alkylene glycols examples include polyethylene glycols, polypropylene glycols, polystyrene (PS), polystyrene (PS), polystyrene (PS), polystyrene (PS), polysulfate, polysulfate, polysulfate, polysulfate, polysulfate, poly(ethylene glycol) ethoxysilyl)
• THF tetrahydrofuran
• the solvent is a glycolic solvent, particularly an alkylene glycol.
• the alkylene glycol may be a monoalkylene glycol, a dialkylene glycol, a trialkylene glycol or a polyalkylene glycol.
• the solvent is an alkylene glycol wherein the alkyl group is a C 2 -C 12 alkyl group, preferably a C 2-8 alkyl group, more preferably a C 2-5 alkyl group such as ethylene, propylene or butylene.
• the solvent may preferably be ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol or propylene glycol.
• the solvent is ethylene glycol.
• the present invention also provides, in a second aspect, a formulation consisting essentially of the reaction product of a THP + salt and an alkylphosphonic acid, wherein the ratio of said THP + salt to said alkylphosphonic acid is from 1: 1 to 750: 1.
• the ratio of THP + to alkylphosphonic acid is preferably from 10: 1 to 500: 1, more preferably from 15: 1 to 300: 1, as from 20: 1 to 100: 1, for example from 25: 1 to 75: 1, most preferably from 30: 1 to 60: 1, for example from 35: 1 to 55: 1, as from 40: 1 to 50: 1.
• the alkylphosphonic acid may suitably be as described above with respect to the first aspect.
• the THP + salt may suitably be as described above with respect to the first aspect.
• the formulations according to the first and second aspects of the invention are particularly useful for preventing the corrosion of ferrous materials (eg, mild steel), copper and aluminum.
• Such formulations may be suitably used to treat a metal sulphide deposit, for example an iron sulphide deposit.
• the iron sulfide may be troilite (FeS) or pyrite (FeS2).
• the iron sulfide may be mackinawite (Fe 9 S 8 ) or pyrrhotite (Fe 7 S 8 ).
• the metal sulfide to be treated may be suitably lead sulfide or zinc sulfide, or a combination thereof.
• Such formulations can also be used as biocides, for treat pests.
• the present invention also provides, in a third aspect, a method for treating an aqueous system while simultaneously inhibiting corrosion of surfaces in contact with said aqueous system, which method comprises simultaneous, sequential or separate addition of an effective amount.
• a THP + salt and an alkylphosphonic acid are simultaneous, sequential or separate addition of an effective amount.
• the treatment may be a treatment to reduce or dissolve a metal sulphide deposit. Therefore, the aqueous system can be a system containing, or in contact with, or sensitive to, a metal sulfide deposit.
• the metal sulphide deposit may be any metal sulphide deposit but, appropriately, it may be iron sulphide.
• the iron sulfide may be troilite (FeS) or pyrite (FeS 2 ).
• the iron sulfide may be mackinawite (FegSg) or pyrrhotite (Fe 7 Sg).
• the metal sulfide may be lead sulfide or zinc sulfide, or a combination thereof.
• the treatment may alternatively or additionally be a biocidal treatment. Therefore, the aqueous system can be a system containing, or in contact with, or sensitive to, harmful microorganisms.
• the alkylphosphonic acid may suitably be as described above with respect to the first aspect.
• the THP + salt may suitably be as described above with respect to the first aspect.
• sufficient alkylphosphonic acid is added to reduce or eliminate corrosion of the surfaces in contact with said aqueous system.
• THP + salt is added to obtain the desired treatment of the aqueous system, e.g. an amount sufficient to reduce or eliminate pests or an amount sufficient to reduce or eliminate metal sulphide deposition.
• the method may include adding a formulation according to the first aspect as described above.
• the aqueous system can be any aqueous system in which the application of a THP + salt can cause corrosion.
• the aqueous system is an improved aqueous oil extraction system.
• the aqueous system can be an aqueous system for industrial water or an aqueous papermaking system.
• the THP + salt is preferably added in an effective amount of up to 30% by weight, preferably from 5% to 30%, for example from 10% to 25% by weight, as from 15% to 20% by weight. weight.
• the alkylphosphonic acid is preferably added in an effective amount of 0.1 to 100000 ppm, based on the volume of the treated system, more preferably from 1 to 10,000 ppm, such as from 10 to 10,000 ppm, for example from 100 to 100 ppm. 1000 ppm.
• Surfaces in contact with said aqueous system may suitably include any metallic material but may include, in particular, ferrous materials (eg, mild steel), copper and / or aluminum.
• the present invention also provides, in a fourth aspect, the use of an alkylphosphonic acid to reduce or prevent the corrosive effect of a THP + salt.
• the alkylphosphonic acid is suitably as described above with respect to the first aspect.
• the THP + salt may suitably be as described above with respect to the first aspect.
• the alkylphosphonic acid may be used in combination with the THP + salt by the use of a formulation according to the first or second aspect of the invention.
• the alkylphosphonic acid can be suitably used in combination with a THP + salt in the form of a solution.
• the solvent may suitably be as described above with respect to the first aspect.
• the use may involve the simultaneous, sequential or separate addition of an alkylphosphonic acid and a THP + salt to a system to be treated.
• the use can be properly applied to the treatment of aqueous systems.
• the use may be in the context of the treatment of an aqueous system containing or in contact with a metal sulphide deposit.
• the use may be in the context of the treatment of an aqueous system containing or in contact with harmful microorganisms.
• the use may adequately involve inhibiting the corrosion of surfaces in contact with the aqueous system.
• Surfaces in contact with said aqueous system may suitably include any metallic material but may include, in particular, ferrous materials (eg, mild steel), copper and / or aluminum.
• the present invention also proposes, in a fifth aspect, the use of a formulation according to the first or second aspect of the invention for the reduction, elimination or prevention of metal sulphide deposition and reduction, elimination or prevention of corrosion.
• the alkylphosphonic acid may suitably be as described above with respect to the first aspect.
• the THP + salt may suitably be as described above with respect to the first aspect.
• the use can be properly applied to the treatment of aqueous systems.
• the use may be in the context of the treatment of an aqueous system containing or in contact with a metal sulphide deposit.
• the use may adequately involve inhibiting the corrosion of surfaces in contact with the aqueous system.
• Surfaces in contact with said aqueous system may suitably include any metallic material but may include, in particular, ferrous materials (eg, mild steel), copper and / or aluminum.
• the use may be to treat an aqueous system containing or in contact with a metal sulphide deposit while simultaneously inhibiting the corrosion of surfaces in contact with said aqueous system.
• the aqueous system can be any aqueous system in which the application of a THP + salt can cause corrosion.
• the aqueous system is an improved aqueous oil extraction system.
• the aqueous system can be an aqueous system for industrial water or an aqueous papermaking system.
• the metal sulphide deposit may be any metal sulphide deposit but, appropriately, it may be iron sulphide.
• the iron sulfide may be troilite (FeS) or pyrite (FeS 2 ).
• the iron sulfide may be mackinawite (Fe 9 S 8 ) or pyrrhotite (Fe 7 S 8 ).
• the metal sulfide may be suitably lead sulfide or zinc sulfide, or a combination thereof.
• the present invention also proposes, in a sixth aspect, the use of a formulation according to the first or second aspect of the invention for the reduction, elimination or prevention of harmful microorganisms and the reduction, elimination or prevention of corrosion.
• the alkylphosphonic acid may suitably be as described above with respect to the first aspect.
• the THP + salt may suitably be as described above with respect to the first aspect.
• the use can be properly applied to the treatment of aqueous systems.
• the use may be in the context of the treatment of an aqueous system containing or in contact with harmful microorganisms.
• the use may adequately involve inhibiting the corrosion of surfaces in contact with the aqueous system.
• Surfaces in contact with said aqueous system may suitably include any metallic material but may include, in particular, ferrous materials (eg, mild steel), copper and / or aluminum.
• the use may be to treat an aqueous system containing or in contact with harmful microorganisms while simultaneously inhibiting the corrosion of surfaces in contact with said aqueous system.
• the aqueous system can be any aqueous system in which the application of a THP + salt can cause corrosion.
• the aqueous system is an improved aqueous oil extraction system.
• the aqueous system can be an aqueous system for industrial water or an aqueous papermaking system.
• the present invention provides, in a seventh aspect, the use of an alkylphosphonic acid in combination with a THP + salt to improve the biocidal efficacy of THP + salt.
• the alkylphosphonic acid may suitably be as described above with respect to the first aspect.
• the THP + salt may suitably be as described above with respect to the first aspect.
• the alkylphosphonic acid may be used in combination with the THP + salt by the use of a formulation according to the first or second aspect of the invention.
• the use adequately concerns the treatment of an aqueous system containing or in contact with harmful microorganisms.
• the microorganisms may in particular be general heterotrophic bacteria.
• the use may involve the simultaneous, sequential or separate addition of an alkylphosphonic acid and a THP + salt to a system to receive a biocidal treatment.
• the alkylphosphonic acid can be suitably used in combination with a THP + salt in the form of a solution.
• the solvent may suitably be as described above with respect to the first aspect.
• the alkylphosphonic acid may be suitably used in combination with a THP + salt for contacting a system containing or in contact with harmful microorganisms.
• the THP + acid and salt may be contacted with the system for any suitable duration, for example 10 seconds or more, such as 30 seconds or more, preferably 45 seconds or more, more preferably one minute or more, for example from one minute to four minutes or more, preferably one and a half minutes or more, for example from two minutes to three minutes or more.
• Aqueous solutions of THPS were tested on mild steel specimens at 50 ° C. for 24 hours to evaluate the corrosion control effect of various agents, which included compounds generally known as inhibitors and alkylphosphonic acid.
• Each solution included an active solution of THPS at 50% by weight plus 1% by weight of a "potential corrosion control agent". The effect of corrosion on mild steel specimens was measured.
• Example 2 A solution of THPS and octylphosphonic acid (OPA) in ethylene glycol was tested on mild steel specimens at 50 0 C for 24 hours to evaluate the effect of corrosion control. The effect of corrosion on mild steel specimens was measured.
• OPA octylphosphonic acid
• THPS octylphosphonic acid
• OPA octylphosphonic acid
• the experiment was repeated to establish a control by not using active ingredient in the aqueous solution in contact.
• the experiment was also repeated for a comparative test, using an aqueous solution of THPS and a surfactant (250 ml / l of active ingredient).
• an alkylphosphonic acid is surprisingly effective in increasing the biocidal effect of a THP + salt, a solution of a THP + salt and an acid. alkylphosphonic acid allowing a greater reduction of bacteria than a solution of a THP + salt and a surfactant.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Life Sciences & Earth Sciences (AREA)
• Organic Chemistry (AREA)
• Materials Engineering (AREA)
• Mechanical Engineering (AREA)
• Metallurgy (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Environmental & Geological Engineering (AREA)
• Hydrology & Water Resources (AREA)
• Water Supply & Treatment (AREA)
• Agronomy & Crop Science (AREA)
• Pest Control & Pesticides (AREA)
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• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
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• Preventing Corrosion Or Incrustation Of Metals (AREA)

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• 2005
  • 2005-11-10 GB GB0522943A patent/GB2432154B/en not_active Expired - Fee Related
• 2006
  • 2006-11-09 WO PCT/EP2006/068291 patent/WO2007054536A1/fr active Application Filing
  • 2006-11-09 US US12/093,319 patent/US8404181B2/en not_active Expired - Fee Related
  • 2006-11-09 BR BRPI0618461-8A patent/BRPI0618461A2/pt not_active IP Right Cessation
  • 2006-11-09 EP EP06819368A patent/EP1966097A1/fr not_active Withdrawn
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