WO2018093244A1 - Inhibiteurs de corrosion et procédés d'utilisation de ces inhibiteurs de corrosion - Google Patents

Inhibiteurs de corrosion et procédés d'utilisation de ces inhibiteurs de corrosion Download PDF

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Publication number
WO2018093244A1
WO2018093244A1 PCT/MY2017/050073 MY2017050073W WO2018093244A1 WO 2018093244 A1 WO2018093244 A1 WO 2018093244A1 MY 2017050073 W MY2017050073 W MY 2017050073W WO 2018093244 A1 WO2018093244 A1 WO 2018093244A1
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composition
fluid stream
fluid
ppm
group
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PCT/MY2017/050073
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Azmi Mohammed NOR
Muhammad Firdaus SUHOR
M Farid MOHAMED
Ahmad Zaki ABAS
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Petroliam Nasional Berhad (Petronas)
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Publication of WO2018093244A1 publication Critical patent/WO2018093244A1/fr

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
    • 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
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
    • 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
    • C23F11/18—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 inorganic inhibitors
    • C23F11/182—Sulfur, boron or silicon containing compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
    • C09K2208/32—Anticorrosion additives

Definitions

  • the present invention generally relates to corrosion inhibitors and methods of using the same.
  • Corrosion of steel or other metallic alloys occurring during the transport of hydrocarbon fluids is a problem faced by the petrochemical industry in general. Steel corrosion may erode and compromise the structural integrity of transportation piping over a period of time if left unchecked. Additionally, the extent of corrosion may be exacerbated by the presence of acidic or basic compounds in the fluid streams being transported within these steel conduits.
  • surfaces which are susceptible to corrosion may be coated or embedded with a protective or sacrificial metal layer which oxidizes preferentially to the surface material.
  • a protective or chemically inert coating may also be applied to the surface to act as a physical barrier between the surface and the corrosive environment.
  • Corrosion inhibitors usually act by adsorption to the surface to be protected and may possess one or more functional groups capable of repelling the corrosive elements present in the fluid flow. In some instances, corrosion inhibitors are injected
  • SUBSTITUTE SHEET RULE 26 intermittently or continuously in controlled amounts into a body of flowing fluid.
  • polyvinyls and polyesters have been demonstrated to provide particularly useful corrosion inhibitors for protecting carbon steel that is exposed to acidic flow conditions.
  • a composition comprising at least one substituted imidazoline and a thiosulfate salt.
  • the disclosed composition may be suitable for use as a corrosion inhibitor.
  • the disclosed composition may serve as a corrosion inhibitor for preventing or reducing corrosion of a metal surface that is being exposed to supercritical fluid flow, e.g., supercritical carbon dioxide (C0 2 ).
  • supercritical fluid flow e.g., supercritical carbon dioxide (C0 2 ).
  • C0 2 supercritical carbon dioxide
  • the disclosed composition may be advantageously suited for use in reducing corrosion rate under fluid environments with C0 2 partial pressure of up to 150 bars.
  • the metal surface may refer to a steel surface, or a carbon steel surface, or other alloys of steel thereof.
  • the substituted imidazoline may comprise at least one polar moiety and at least one non-polar moiety.
  • the non-polar moiety may be a hydrophobic group or an electron-donating group.
  • the polar moiety anchors the imidazoline to the metal surface to be protected (e.g., a steel surface), while the imidazoline is sterically arranged or configured to present the non-polar / electron-donating moiety (e.g., long-chain alkyl) in an orientation normal to the surface to which the imidazoline is anchored.
  • the arrangement of the hydrophobic or non-polar moiety helps to repel reactive species from contacting or reacting with the metal surface, thereby preventing electrochemical corrosion.
  • the polar group may allow the imidazoline to form in situ a protective film layer that is coupled to the metal surface.
  • the film layer may be substantially uniform in thickness.
  • the film layer may also be electrostatically bound to the metal surface due to the presence of the polar group.
  • the type of imidazoline is not particularly limited and it is expected that suitable technical variants and derivatives of imidazoline would be known to one ordinarily skilled in the art. Nonetheless, the present disclosure exemplifies at least one corrosion inhibitor composition comprising a substituted imidazoline in combination with the thiosulfate salt.
  • the disclosed composition is capable of providing a reduced corrosion rate of the metal surface that has been exposed to or is in contact with a supercritical fluid, e.g., supercritical C0 2 and water.
  • the reduced corrosion rate of the metal surface may be less than 0.5 mm/year, less than 0.4, less than 0.3, less than 0.2, less than 0.1, less than 0.09, less than 0.08, less than 0.07, less than 0.06, or less than 0.05 mm/year.
  • the reduced corrosion rate may be from about 0.01 - 0.2, from about 0.01 to about 0.1, from about 0.01 to about 0.05, from about 0.01 to about 0.025 mm/year.
  • the corrosion rate may be
  • SUBSTITUTE SHEET RULE 26 advantageously be from 0 to 0.1 mm/year under the above described high C0 2 partial pressure conditions.
  • the supercritical fluid may comprise supercritical carbon dioxide and water.
  • the supercritical fluid may comprise essentially of supercritical carbon dioxide, that is, the bulk of the fluid is supercritical carbon dioxide and wherein trace amounts of water may be present.
  • the supercritical fluid may consist essentially of supercritical carbon dioxide.
  • the disclosed corrosion inhibitor comprising the substituted imidazoline and the thiosulfate salt has been found to be particularly effective in preventing or reducing corrosion of steel surfaces that are in contact with water-containing supercritical carbon dioxide.
  • Another aspect of the present invention relates to a method for inhibiting or reducing corrosion of a metal surface, the method comprising a step of contacting the metal surface with a corrosion inhibitor composition comprising a substituted imidazoline and a thiosulfate salt.
  • the metal surface may be one that is constantly, intermittently or periodically exposed to a supercritical fluid.
  • the method may comprise contacting the metal surface with a corrosion inhibitor composition that is disclosed herein.
  • the disclosed method may be advantageously suited for inhibiting or reducing corrosion of metal surfaces that are exposed to or under high pressure, high temperature or supercritical fluid flow conditions.
  • the disclosed method may be advantageously suited for inhibiting or reducing corrosion of metal surfaces exposed to supercritical carbon dioxide.
  • the disclosed method and composition may inhibit or reduce corrosion rates at fluid flow pressure of up to 150 bars and a fluid flow temperature of up to 100 °C.
  • the disclosed method and corrosion inhibitor composition may be capable or inhibiting or reducing corrosion of metal surfaces exposed to fluids having a C0 2 partial pressure of from about greater than 0 bars to about 150 bars, about 10 to about 150 bars, about 20 to about 150 bars, about 30 to about 150 bars, about 40 to about 150 bars, about 50 to about
  • SUBSTITUTE SHEET RULE 26 150 bars, about 60 to about 150 bars, about 70 to about 150 bars, about 80 to about 150 bars, about 90 to about 150 bars, about 100 to about 150 bars, about 110 to about 150 bars, about 120 to about 150 bars, about 130 to about 150 bars, or about 140 to about 150 bars.
  • each disclosed pressure range may be subject to a variance of about ⁇ 9, ⁇ 8, ⁇ 7, ⁇ 6, ⁇ 5, ⁇ 4, ⁇ 3, ⁇ 2 or ⁇ 1 bar.
  • alkyl when used herein, refers to a linear or branched, optionally substituted, saturated hydrocarbon group having from 1 to 40 carbon atoms.
  • exemplary alkyl groups include but are not limited to methyl, ethyl, 1-propyl, isopropyl, 1-butyl, 2-butyl, isobutyl, tert-butyl, amyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, pentyl, isopentyl, hexyl, 4- methylpentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylbutyl, 3,3- dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1,2,2-trimethylpropyl, 1, 1,2- trimethylpropyl, 2-ethylpentyl, 3-ethylpentyl, heptyl, 1-methylhexyl,
  • heteroalkyl when used herein, refers to an alkyl group wherein one or more carbon atoms are replaced by an oxygen-, nitrogen-, phosphorus, boron or sulphur atom.
  • heteroalkenyl and “heteroalkynyl” shall be construed accordingly.
  • alkenyl when used herein, refers to straight chain or branched chain unsaturated aliphatic groups containing at least one carbon-carbon double bond and having from 2 to 20 carbon atoms.
  • exemplary alkenyl groups may include but are not limited to ethenyl, propenyl, butenyl, 1-butenyl, 2-butenyl, 2-methylpropenyl, 1-pentenyl, 2-pentenyl, 2- methylbut-l-enyl, 3-methylbut- l-enyl, 2-methylbut-2-enyl, 1-hexenyl, 2-hexenyl, 3-
  • alkynyl when used herein, refers to a hydrocarbon group having at least 2 to 30 carbon atoms and containing at least one carbon-carbon triple bond.
  • optionally substituted as used herein means the group to which this term refers may be unsubstituted, or may be substituted with one, two, three or more groups other than hydrogen provided that the indicated atom's normal valency is not exceeded, and that the substitution results in a stable compound.
  • Such groups may be, for example, halogen, hydroxy, oxo, cyano, nitro, alkyl, alkoxy, haloalkyl, haloalkoxy, aryl alkoxy, alkylthio, hydroxyalkyl, alkoxyalkyl, cycloalkyl, cycloalkylalkoxy, alkanoyl, alkoxycarbonyl, alkylsulfonyl, alkylsulfonyloxy, alkylsulfonylalkyl, arylsulfonyl, arylsulf onyloxy , arylsulfonylalkyl, alkylsulfonamido, alkylamido, alkylsulfonamidoalkyl, alkylamidoalkyl, arylsulfonamido, arylcarboxamido, arylsulfonamidoalkyl, arylcarboxa
  • steel' is to be interpreted broadly to include an alloy of iron, carbon and optionally further including one or more elements selected from manganese, nickel, chromium, molybdenum, vanadium, silicon, boron, aluminium, cobalt, copper, cerium, niobium, titanium, tungsten, tin, zinc, lead, and zirconium.
  • the term "steel” should be taken to broadly include crucible steel, carbon steel, alloy steel, and alloys thereof. In one embodiment, the "steel” surfaces referred to in the present disclosure may be "alloy steel".
  • carbon steel refers to steel in which the primary alloying component is carbon and wherein from 0.1 to 3% by weight of the alloy is carbon.
  • supercritical fluid refers to a fluid that is subjected to or existing under a specific set of pressure and temperature conditions, such that the fluid does not possess distinct liquid and gas phases.
  • the temperature and pressure at which a fluid becomes supercritical is termed “critical temperature” and “critical pressure” respectively.
  • critical temperature The temperature and pressure at which a fluid becomes supercritical
  • critical pressure At supercritical conditions, the density possessed by the fluid is also termed its “critical density”.
  • supercritical C0 2 occurs at 304.1k, 72.8 bar and possesses a critical density of 0.469 gem 3 .
  • substituted imidazoline refers to a five-membered heterocyclic compound having a generic structure expressed by
  • substituted imidazoline may include imidazoline compounds comprising at least one polar moiety and at least one hydrophobic moiety.
  • the polar moiety may be provided on position 3 of the heterocycle (i.e., at R2's position).
  • the non-polar or hydrophobic moiety may be provided at position 2 of the heterocycle, i.e., at position Rl.
  • SUBSTITUTE SHEET RULE 26 stated value more typically +/- 3% of the stated value, more typically, +/- 2% of the stated value, even more typically +/- 1% of the stated value, and even more typically +/- 0.5% of the stated value.
  • range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the disclosed ranges. Accordingly, the description of a range should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, description of a range such as from 1 to 6 should be considered to have specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6 etc., as well as individual numbers within that range, for example, 1, 2, 3, 4, 5, and 6. This applies regardless of the breadth of the range.
  • a composition comprising at least one substituted imidazoline and a thiosulfate salt, wherein said substituted imidazoline comprises at least one polar moiety and at least one non-polar or hydrophobic moiety.
  • the substituted imidazoline and the thiosulfate salt may be blended in weight ratios as disclosed herein to form an admixture or a ready-to-use corrosion inhibitor ("CI") formulation.
  • CI ready-to-use corrosion inhibitor
  • suitable additives including but not limited to, excipients, surfactants, solvents, rheological modifiers and carriers may be mixed with the above active ingredients of the disclosed
  • the CI composition comprises about 1% to about 10% by weight of the thiosulfate salt, such as about 1%, about 2%, about 3%, about 4%, about 5%, about 6%, about 7%, about 8%, about 9% or about 10% by weight of the thiosulfate salt.
  • the CI composition may comprise the thiosulfate salt in a range comprising an upper limit and a lower limit selected from any two percentage values disclosed above.
  • the thiosulfate salt may be selected from lithium thiosulfate, potassium thiosulfate or sodium thiosulfate.
  • the disclosed composition comprises about 5% by weight of a sodium thiosulfate.
  • the CI composition comprises about 10% to about 30% by weight of the substituted imidazoline, for example, about 10%, about 11%, about 12%, about 13%, about 14%, about 15%, about 16%, about 17%, about 18%, about 19%, about 20%, about 21%, about 22%, about 23%, about 24%, about 25%, about 26%, about 27%, about 28%, about 29% or about 30% by weight of the substituted imidazoline.
  • the amount of substituted imidazoline contained within the CI composition may be in a range comprising an upper limit and a lower limit selected from any two percentage values disclosed above.
  • the disclosed composition comprises about 30 % by weight of a substituted imidazoline of formula II as further disclosed herein.
  • a particular embodiment of the disclosed CI composition comprises from about 20 wt. % to about 30 wt. % of the substituted imidazoline, about 1 wt. % to about 10 wt. % of the thiosulfate salt and about 40 wt. % to about 89 wt. % of a solvent, wherein the total weight percent is 100 %.
  • a preferred solvent for the disclosed composition is water.
  • a further embodiment of the disclosed CI composition comprises from about 30 wt. % of said imidazoline derivative, about 5 wt. % thiosulfate and about 65 wt. % of the solvent.
  • the solvent may be water.
  • the substituted imidazoline may be a compound having the following formula (I) :
  • Rl is a hydrophobic group
  • R2 is a polar group
  • R3 is H, optionally substituted alkyl, optionally substituted alkene, or optionally substituted alkynyl.
  • Rl may be a non-polar, hydrophobic group.
  • Rl may be optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkene, optionally substituted heteroalkene, or optionally substituted alkynyl.
  • Rl may be a Ci 0 -4o alkyl or a heteroalkyl comprising at least one unsaturated carbon or at least one heteroatom expressing a lone pair of electrons.
  • Rl is a unsubstituted Cio-20 alkenyl group.
  • Rl may be an unsubstituted C 12 i 7 alkenyl group.
  • Rl may be selected from an unsaturated C6-20 alkyl group, C7-20 alkyl group, C8-20 alkyl group, C9- 20 alkyl group, CIO-20 alkyl group, CI 1-20 alkyl group, C12-20 alkyl group, C13-20 alkyl group, C14-20 alkyl group, C- 15-20 alkyl group, C16-20 alkyl group, C17-20 alkyl group, C18-20 alkyl group, or a C19-20 alkyl group.
  • R2 may be a polar moiety comprising at least one polar functional group that expresses electrostatic affinity with a metal surface.
  • R2 may be optionally substituted amino, alkoxy, ether, carbonyl, carboxylate, or optionally substituted alkylacetamide, each group may be optionally attached to the core imidazoline structure via an alkylene bridge.
  • R2 may be a polar group having the following structural
  • R4 and R5 are independently H, halogen, optionally substituted alkyl, haloalkyl, optionally substituted alkenyl and optionally substituted alkynyl.
  • R4 and R5 may be independently selected from methyl, ethyl, propyl, butyl, pentyl or hexyl.
  • the substituted imidazoline for use in the disclosed corrosion inhibitor compositions is a compound having the formula (II):
  • the present disclosure also relates to a method of inhibiting or reducing corrosion on a metal surface being exposed to a flowing fluid stream, the method comprising a step of contacting the metal surface with a corrosion inhibitor composition comprising at least one substituted imidazoline and a thiosulfate salt, or the compositions as disclosed above.
  • the fluid stream may comprise carbon dioxide and water.
  • the water may be present in a liquid state e.g., free-flowing water, or may be present as water vapour, or a mixture thereof.
  • the fluid stream may comprise supercritical carbon dioxide containing trace amounts of water or is saturated with water.
  • the water content may exceed 10,000 ppm.
  • the water content of the fluid stream may be from about 1,000 ppm to about 10,000 ppm.
  • the water content of the fluid stream may be about 1,000 ppm, 2,000 ppm, 3,000 ppm, 4,000 ppm, 5,000 ppm, 6,000 ppm, 7,000 ppm, 8,000 ppm, 9,000 ppm or 10,000 ppm, subject to a variance of
  • the disclosed corrosion inhibitor is capable to reducing corrosion rates to less than 0.5 to 0.05 mm per year.
  • the fluid stream may be characterized by a mixture of carbon dioxide and water, wherein the molar concentration of carbon dioxide may be from about 1 to 99 mol%.
  • the molar concentration (mol %) of C02 may be about 1 mol%, 5 mol%, 10 mol%, 15 mol%, 20 mol%, 25 mol%, 30 mol%, 35 mol%, 40 mol%, 45 mol%, 50 mol%, 55 mol%, 60 mol%, 65 mol%, 70 mol%, 75 mol%, 80 mol%, 85 mol%, 90 mol%, 91 mol%, 92 mol%, 93 mol%, 94 mol%, 95 mol%, 96 mol%, 97 mol%, 98 mol%, or 99 mol%.
  • the molar concentration of C0 2 may be in a range comprising an upper and lower limit selected from any two of the above disclosed values.
  • the fluid stream may be characterized by a partial pressure of C0 2 of from about greater than 0 bar to about 150 bars, and a temperature of about 15 °C to about 100 °C.
  • the fluid stream is subjected to conditions for providing supercritical carbon dioxide, wherein the fluid stream is at critical temperature and critical pressure of carbon dioxide.
  • the flowing fluid stream may be characterized by a C0 2 partial pressure of from about 70+5 - 120+5 bars, and at a temperature of at least 15+5 °C to 80 +5°C.
  • the flowing fluid stream may be characterized by a C0 2 partial pressure of at least 73 bar, and at a temperature of at least 32 °C.
  • the fluid stream may be one that is substantially free of hydrogen sulfide.
  • the contacting step may be accomplished by mixing of the corrosion inhibitor composition with the flowing fluid stream in an amount effective to inhibit or reduce corrosion of the metal surface.
  • the corrosion inhibitor composition may be added to the flowing fluid stream in an amount required to provide a concentration of from about 0.01 ppm to about 500 ppm of the corrosion inhibitor in the fluid flow.
  • the concentration of the corrosion inhibitor in the fluid stream may be about 0.01 ppm, 0.1 ppm, 1 ppm, 10 ppm, 20 ppm, 50 ppm, 100 ppm, 150 ppm, 200 ppm, 250 ppm, 300 ppm, 350 ppm, 400 ppm, 450 ppm or about 500 ppm.
  • the substituted imidazoline is found to be effective under conditions wherein the hydrogen sulfide is present in the fluid stream at a concentration of from about 0.01 to about 500 ppm.
  • a minimal concentration of the corrosion inhibitor has been advantageously found to be sufficient for inhibiting or reducing corrosion rates to a rate of from lesser than 0.5 to lesser than 0.05 mm per year.
  • a concentration of about 0.01 to about 500 ppm e.g., about 0.01 ppm, about 0.1 ppm, about 1 ppm, about 10 ppm, about 20 ppm, about 50 ppm, about 100 ppm, about 150 ppm, about 200 ppm, about 250 ppm, about 300 ppm, about 350 ppm, about 400 ppm, about 450 ppm or about 500 ppm of the corrosion inhibitor (without thiosulfate salt) is sufficient for achieving the desired protection.
  • the present disclosure further relates to the use of a corrosion inhibitor composition or a imidazoline-based corrosion inhibitor as described herein for inhibiting or reducing corrosion of a metal surface, in particular, a steel surface that is exposed to a fluid or a supercritical fluid disclosed herein.
  • the present disclosure further provides a system for transporting a fluid, said system comprising at least one metal conduit for conveying said fluid therethrough, and wherein said system comprises at least one inlet means that is fluidly communicated with a source of a corrosion inhibitor composition as defined herein, and wherein said inlet means is configured to discharge the corrosion inhibitor composition into the fluid during transport.
  • the corrosion inhibitor composition used in such a system may comprise a substituted imidazoline and a thiosulfate salt.
  • the inlet means may be fluidly communicated with a
  • the transported fluid may consists essentially of supercritical C0 2 , or water- containing supercritical C0 2 or water- saturated supercritical C0 2 .
  • the disclosed system may be particularly useful for transporting a supercritical fluid, including supercritical carbon dioxide.
  • the disclosed system may be transporting a stream of supercritical C0 2 having a water content in an amount of from 1000 ppm to 7,000 ppm.
  • the disclosed systems may further comprise metering means acting in cooperation with said inlet means and configured to discharge the required doses of the corrosion inhibitor composition or the substituted imidazoline to achieve a desired concentration of the corrosion inhibitor in the flowing fluid.
  • the corrosion inhibitor composition may be admixed with a feed fluid stream prior to being conveyed to the steel conduit. This may be accomplished via a flow mixer installed upstream of the metal conduit.
  • the corrosion inhibitor may be introduced via one or more separate inlets, each inlet being fluidly communicated with the steel conduit.
  • the corrosion inhibitor composition may be introduced in a single dose or repeatedly via multiple doses.
  • the corrosion inhibitor may also be introduced to the fluid stream by a plurality of inlets disposed along a length between an upstream section and a downstream section of the metal conduit.
  • FIG. 1 is a schematic diagram representing a truncated section of a sub-sea pipe transporting a fluid dosed with a corrosion inhibitor composition as disclosed herein.
  • FIG. 2 is a graph showing the comparative experimental results of the performance of a corrosion inhibitor according to the present invention (Line A) compared to conventional inhibitors (Lines B and C) and a control (Line D).
  • Fluid stream 2 comprises supercritical carbon dioxide that is water-saturated. Water saturation of supercritical carbon dioxide may occur at a water content of around 7,000 ppm H 2 0. The fluid stream 2 is otherwise composed essentially of supercritical carbon dioxide.
  • the pipe 12 may comprise at least an upstream section extending above sea level (denoted by line 8a) and a downstream section submerged below the water surface and disposed in proximity and in parallel to the sea bed (denoted by line 8b).
  • the fluid stream 2 flowing through the upstream section may have a temperature of around 80 °C and may also possess a C0 2 partial pressure of around 120 bar.
  • the lower circumference of the pipe 12 may come into contact with water entrained within the fluid 2.
  • the water may be due to carry-over from an earlier process or may be due to condensation.
  • the carry-over water may accumulate at a base region 4a of the pipe 12. Region 4a is therefore at substantial risk of corrosion under normal operating conditions.
  • region 4b denotes a section of the pipe that may be susceptible to bottom of the line corrosion. Such corrosion is typically caused by the accumulation of water due to entrainment at the flow boundaries. The presence of water may also be due to the condensation as the submerged section of the pipe 12 experiences a lower ambient
  • the downstream fluid stream 14 may possess a carbon partial pressure of around 80 bars and a temperature of around 25 °C.
  • the pipe may be fluidly communicated with a source of the corrosion inhibitor composition as disclosed herein.
  • the corrosion inhibitor composition may be discharged into the fluid stream 2 prior to ingress into the pipe.
  • the dosing may be a batch operation.
  • one or more additional inlets may be installed along the length of the pipe for injection of plural doses of the corrosion inhibitor composition.
  • a pipe transporting fluid that has not been dosed with a corrosion inhibitor disclosed herein may experience corrosion at the corrosion-susceptible regions at a rate of more than 80 mm per year. Conversely, it has been observed that a pipe subjected to similar flow conditions and comparable periods of exposure may exhibit a corrosion rate of 0.5 mm per year or less when the transported fluid has been dosed with a corrosion inhibitor composition as disclosed herein.
  • FIG. 2 A set of comparative experimental results are shown in Fig. 2.
  • the performance (measured by corrosion rate, mm/year) of a corrosion inhibitor composition according to the present invention comprising a substituted imidazoline (Formula II) and sodium thiosulfate (Product A) is being compared against conventional CI compositions product B and product C.
  • Line D of Figure 2 shows the corrosion rate (uninhibited) wherein no corrosion inhibitor has been added.
  • the testing conditions are as follows:
  • Fluid / Gas flow composition C0 2 gas with water (70 mol. %)
  • Fluid / gas flow conditions 120 bar, 80 °C Compositions A-C:
  • Supercritical carbon dioxide is commonly used as cleaning agents, solvents or as extracting agents in industrial chemical processes. Hence, increasingly, there is a need to provide or install equipment or piping for either the storage or transport of supercritical carbon dioxide.
  • the maintenance of such systems requires a suitable formulation for protecting such equipment and modules from corrosion. This in turn extends the plant file and reduces down time for maintenance and replacement of parts.
  • the disclosed corrosion inhibitor composition has been shown to possess unique utility in reducing or inhibiting corrosion of metal surfaces, in particular, steel surfaces when exposed to supercritical fluids including water-saturated supercritical fluids.
  • the disclosed compositions may therefore be applied in a wide variety of petrochemical and pharmaceutical processes requiring the transport of supercritical fluids.
  • the disclosed corrosion inhibitor may be advantageously applied in and to subsea piping systems transporting supercritical C0 2 -

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  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

La présente invention concerne une composition ou une formulation d'inhibiteur de corrosion comprenant au moins un composé imidazoline substitué et au moins un sel de thiosulfate. La présente invention concerne en outre l'utilisation des compositions ou des formulations de l'invention comme inhibiteurs de corrosion dans des systèmes de transport de fluide, en particulier pour une utilisation dans des tuyaux en acier.
PCT/MY2017/050073 2016-11-18 2017-11-20 Inhibiteurs de corrosion et procédés d'utilisation de ces inhibiteurs de corrosion WO2018093244A1 (fr)

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CN109609110A (zh) * 2018-11-29 2019-04-12 中国石油天然气股份有限公司 一种co2驱油用缓蚀清垢剂及制备方法和使用方法
CN111504893A (zh) * 2020-05-19 2020-08-07 北京科技大学 一种低含水率、超临界或密相二氧化碳腐蚀模拟的装置及其使用方法和应用
WO2020185569A1 (fr) 2019-03-08 2020-09-17 Baker Hughes Oilfield Operations Llc Contrôle de la corrosion pour dioxydes de carbone supercritiques

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CN104630784A (zh) * 2015-02-09 2015-05-20 西安华诺石油技术开发有限公司 一种抗二氧化碳缓蚀剂及其制备方法
WO2016092010A1 (fr) * 2014-12-11 2016-06-16 Clariant International Ltd Composition inhibitrice liquide, son procédé de préparation et son utilisation dans le cadre de la lutte contre la corrosion par la saumure lourde

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US20090131283A1 (en) * 2007-11-15 2009-05-21 Nguyen Duy T Imidazoline-based heterocyclic foamers for downhole injection
CN101838811A (zh) * 2009-03-20 2010-09-22 杨江 石油生产用新型特种缓蚀剂
WO2016092010A1 (fr) * 2014-12-11 2016-06-16 Clariant International Ltd Composition inhibitrice liquide, son procédé de préparation et son utilisation dans le cadre de la lutte contre la corrosion par la saumure lourde
CN104630784A (zh) * 2015-02-09 2015-05-20 西安华诺石油技术开发有限公司 一种抗二氧化碳缓蚀剂及其制备方法

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CANTO MAYA, C. M.: "Effect of Wall Shear Stress on Corrosion Inhibitor Film Performance", A DISSERTATION PRESENTED TO THE FACULTY OF THE RUSS COLLEGE OF ENGINEERING AND TECHNOLOGY OF OHIO UNIVERSITY, December 2015 (2015-12-01) *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109609110A (zh) * 2018-11-29 2019-04-12 中国石油天然气股份有限公司 一种co2驱油用缓蚀清垢剂及制备方法和使用方法
CN109609110B (zh) * 2018-11-29 2021-03-09 中国石油天然气股份有限公司 一种co2驱油用缓蚀清垢剂及制备方法和使用方法
WO2020185569A1 (fr) 2019-03-08 2020-09-17 Baker Hughes Oilfield Operations Llc Contrôle de la corrosion pour dioxydes de carbone supercritiques
US11142831B2 (en) 2019-03-08 2021-10-12 Baker Hughes Oilfield Operations Llc Corrosion control for supercritical carbon dioxide fluids
EP3935203A4 (fr) * 2019-03-08 2022-11-16 Baker Hughes Oilfield Operations LLC Contrôle de la corrosion pour dioxydes de carbone supercritiques
CN111504893A (zh) * 2020-05-19 2020-08-07 北京科技大学 一种低含水率、超临界或密相二氧化碳腐蚀模拟的装置及其使用方法和应用

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