WO2019217496A1 - Mélanges d'inhibiteurs de corrosion - Google Patents

Mélanges d'inhibiteurs de corrosion Download PDF

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Publication number
WO2019217496A1
WO2019217496A1 PCT/US2019/031224 US2019031224W WO2019217496A1 WO 2019217496 A1 WO2019217496 A1 WO 2019217496A1 US 2019031224 W US2019031224 W US 2019031224W WO 2019217496 A1 WO2019217496 A1 WO 2019217496A1
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WIPO (PCT)
Prior art keywords
corrosion inhibitor
kinetic
thermodynamic
composition
corrosion
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PCT/US2019/031224
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English (en)
Inventor
Trevor Lloyd Hughes
Lynne Patricia Crawford
Man Yi HO
Evgeny Barmatov
Jill F. Geddes
Paul Barnes
Tore NORDVIK
Original Assignee
Schlumberger Technology Corporation
Schlumberger Canada Limited
Services Petroliers Schlumberger
Schlumberger Technology B.V.
Schlumberger Norge As
M-I Drilling Fluids U.K. Ltd.
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Publication of WO2019217496A1 publication Critical patent/WO2019217496A1/fr

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    • 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
    • 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
    • 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 downhole environment presents harsh operating conditions for downhole equipment, including high temperatures, caustic chemicals, and constrained spacing.
  • the downhole conditions can cause impediments such as equipment corrosion and scaling that can damage downhole tools and impact tool function.
  • Downhole scale also may lead to a reduction in productivity or performance due to obstructed flow passages.
  • compositions that include a corrosion inhibitor blend including: a kinetic corrosion inhibitor and a thermodynamic corrosion inhibitor, wherein the kinetic corrosion inhibitor has a rate of film formation that is at least 1.5 times greater than the respective rate of film formation of a thermodynamic corrosion inhibitor on a metal surface.
  • embodiments disclosed herein relate to methods that may include contacting a metal surface with a corrosion inhibitor composition, wherein the corrosion inhibitor composition includes: a kinetic corrosion inhibitor and a thermodynamic corrosion inhibitor, wherein the kinetic corrosion inhibitor has a rate of film formation that is at least 1 5x greater than the respective rate of film formation of a thermodynamic corrosion inhibitor on a metal surface.
  • FIG. 1 is a histogram of carbon chain length for a number of natural acid sources in accordance with embodiments of the present disclosure.
  • FIG. 2 is a graphical representation depicting polarization resistance as a function of time for a number of corrosion inhibitor compositions in accordance with embodiments of the present disclosure.
  • FIG. 3 is a bar chart depicting the cumulative inverse polarization resistance for a number of corrosion inhibitor compositions in accordance with embodiments of the present disclosure.
  • FIG. 4 is a graphical representation depicting the initial slope of the polarization resistance profile for a number of corrosion inhibitors in accordance with embodiments of the present disclosure.
  • FIG 5 is a graphical representation depicting polarization resistance as a function of time for a number of corrosion inhibitor compositions in accordance with embodiments of the present disclosure.
  • FIG. 6 is a bar chart depicting the cumulative inverse polarization resistance for a number of corrosion inhibitor compositions in accordance with embodiments of the present disclosure.
  • FIG. 7 is a bar chart showing cumulative corrosion rates after 48 hours of exposure for a number of corrosion inhibitor compositions in accordance with embodiments of the present disclosure.
  • FIG. 8 is a graphical representation depicting polarization resistance as a function of time for a number of corrosion inhibitor compositions in accordance with embodiments of the present disclosure.
  • FIG. 9 is a graphical representation depicting change in polarization resistance over change in time as a function of kinetic inhibitor in a blend of inhibitors in accordance with embodiments of the present disclosure.
  • FIG. 10 is a graphical representation depicting the final polarization resistance as a function of thermodynamic inhibitor for a number of corrosion inhibitor compositions in accordance with embodiments of the present disclosure.
  • FIG. 11 is a graphical representation depicting polarization resistance as a function of time for a number of corrosion inhibitor compositions in accordance with embodiments of the present disclosure.
  • FIG. 12 is a bar chart showing cumulative corrosion rates after 48 hours of exposure for a number of corrosion inhibitor compositions in accordance with embodiments of the present disclosure.
  • embodiments disclosed herein relate to blends of corrosion inhibitors that prevent or mitigate the corrosion of metals, including metal materials and equipment employed in wellbore operations and similar processes where corrosive fluids and/or gases are present in process streams.
  • Corrosion inhibitor compositions in accordance with the present disclosure may exhibit surfactant and electrostatic properties that enable film formation on metal surfaces even at elevated temperatures, increasing treatment duration and minimizing the effective concentration needed to treat corrosion.
  • corrosion inhibitor compositions may include a synergistic mixture of kinetic corrosion inhibitors and thermodynamic corrosion inhibitors that work together to form protective films quickly and having greater durability than either corrosion inhibitor alone.
  • Corrosion describes reaction processes that occur over relatively long time frames when metals and other materials are exposed to corrosive agents in the surrounding environment. Corrosion affects metal tool surfaces and tubing in contact with petroleum, acids, caustics, and other compounds present in injected and produced fluids, which can lead to damage and failure of downhole equipment. Similarly, equipment used to handle and transport corrosive fluids at the surface and within pipelines may be affected by corrosion. Reactive surfaces are often treated with corrosion inhibitors by coating or by addition to process streams contacting the surfaces.
  • metal surfaces may be exposed to corrosive production fluids and mixtures of acidic gases for ranges of time that may span months to years, which underlines the importance of maintaining a persistent film using a protective dosage of corrosion inhibitors continuously injected into the evolving production fluids.
  • the ratio of hydrocarbon to brine obtained from the well may change over time, which may require re-evaluation and adjustments to optimize the corrosion inhibitor formulation and the target dosage.
  • corrosion inhibitors may be subdivided into groups of“kinetic corrosion inhibitors” and“thermodynamic corrosion inhibitors” based on (1) rates of film formation on metal surfaces and/or (2) persistence of formed films over time.
  • kinetic corrosion inhibitors form films more rapidly than thermodynamic corrosion inhibitors, while thermodynamic corrosion inhibitors tend to form films that are more stable over time in corrosive environments and in high temperature high pressure (HTHP) applications.
  • HTHP high temperature high pressure
  • corrosion inhibitors in accordance with the present disclosure may have a general structure defined by at least one polar heterocyclic head group and a hydrophobic chain or spacer group, and may prevent or minimize corrosion by forming a hydrophobic barrier film that isolates metal surfaces through physisorption and/or chemisorption. While not limited to a particular theory, it is believed that the polar head groups may interact with metal surfaces, anchoring the inhibitor molecule, while a hydrophobic chain is responsible for film formation through hydrophobic interactions with neighboring molecules.
  • Corrosion of metals in wellbore operations at the surface and downhole is initiated by electrochemical reactions that occur when the surface becomes polarized, often in the presence of ionic liquids such as aqueous salt solutions.
  • Corrosion inhibitors and other treatments increase the ability of metal surfaces to resist polarization and, in turn, resist the initiation and propagation of corrosive reactions.
  • corrosion inhibitors may be classified as kinetic or thermodynamic corrosion inhibitors based on the comparative film formation rates of the respective corrosion inhibitors on a metal surface such as steel or other industrial metals.
  • kinetic corrosion inhibitors may form films at a rate that is at least 1.5 times greater than that of a thermodynamic corrosion inhibitor incorporated into a corrosion inhibitor blend.
  • the comparative film formation rates may be calculated using any film characterization method and at any temperature or fluid composition.
  • rates of film formation by kinetic and thermodynamic corrosion inhibitors may be characterized by the increase in resistance to polarization (R p ) of a treated metal surface over time (5R p /5t).
  • R p resistance to polarization
  • 5R p /5t standards may be based on the corresponding relative values obtained from standardized corrosion tests including ASTM G185, ASTM G102, ASTM G170 and other electrochemical tests for metal corrosion.
  • the kinetic inhibitors may have a 5R p /5t that is at least 1.5 times that of the thermodynamic inhibitor, or at least 2 times in more particular embodiments.
  • kinetic corrosion inhibitors may be classified by those compounds having a 5R p /5t of > 150 when applied to a metal surface alone or as a blend, where R p is in units of Ohm and t is in units of hours during the first two hours after treatment of a rotating cylinder electrode at 70 °C in a C0 2 -saturated brine containing 3 wt% NaCl and 143 mM of the corrosion inhibitor or blend, using the detailed test procedures described in the Examples below. Further, it is also understood that such detailed test procedure may be used to determine the relative film formation rate or 5R p /5t discussed above.
  • corrosion inhibitors may be classified by the long term resistance, 24 hours after treatment, of films applied to a metal surface as characterized by R p measured after treatment of a rotating cylinder electrode at 70 °C in a C0 2 -saturated brine containing 3 wt% NaCl.
  • a thermodynamic corrosion inhibitor in a blend may be defined as an inhibitor exhibiting a long term R p that is > 2 times greater than the respective kinetic inhibitor in the blend.
  • a thermodynamic corrosion inhibitor in a blend may be defined as an inhibitor exhibiting a long term R p that is > 3 to 4 times greater than the respective kinetic inhibitor in the blend.
  • the long term resistance (after 24 hours) may be measured using the test procedures detailed below, the standardized corrosion resistance tests such as ASTM G185, ASTM G102, ASTM G170 and other electrochemical tests for metal corrosion may also be used to determine the relative R p values.
  • corrosion inhibitors may be classified by structural features such as the length of a hydrophobic chain present on the inhibitor molecule.
  • “kinetic corrosion inhibitors” may be defined as corrosion inhibitors having hydrophobic chains that are saturated or partially unsaturated and include a number of carbon atoms that ranges between 2 and 14; and“thermodynamic corrosion inhibitors” may be defined as corrosion inhibitors having hydrophobic chains that are saturated or partially unsaturated and include a number of carbon atoms that ranges between 15 and 30.
  • corrosion inhibitor compositions may include blends of corrosion inhibitors having a balance of film forming properties.
  • film formation and film strength may be optimized by adjusting the relative ratios of kinetic inhibitors and thermodynamic inhibitors.
  • Corrosion inhibitor blends may be optimized based in part on the composition and structure of the hydrophobic tail group (or groups).
  • Corrosion inhibition rates may also be tuned by varying the chemistry of the heterocyclic polar head group.
  • polar head groups of kinetic inhibitors and thermodynamic inhibitors may be the same or different.
  • Methods in accordance with the present disclosure may include the use of corrosion inhibiting compositions in corrosive environments, including those created during hydrocarbon production and other wellbore applications in which metal surfaces are exposed to multi-phase process streams having mixtures of gases, brines, and hydrocarbon phases.
  • Corrosion inhibitor compositions in accordance with the present disclosure may be used to protect metal surfaces exposed to process streams flowing from a reservoir to the surface and beyond.
  • corrosion inhibitor compositions may be used to minimize the corrosion of exposed surfaces in wellbore operations such as decking, wellbore casing, tubulars, drill strings, and other downhole equipment.
  • Corrosion inhibitor compositions in accordance with the present disclosure may include a mixture of kinetic and thermodynamic corrosion inhibitors.
  • corrosion inhibitors may include organic compounds may have a general structure that include a polar heterocyclic head group containing electron-rich heteroatoms, and a hydrophobic tail group composed of a saturated or unsaturated hydrocarbon chain.
  • corrosion inhibitors may be classified as kinetic corrosion inhibitors having a C2 to C14 hydrocarbon chain, and thermodynamic corrosion inhibitors having a C15 to C30 hydrocarbon chain.
  • corrosion inhibitor compositions may be modified by adjusting the polar heterocyclic head group chemistry of the kinetic and/or thermodynamic corrosion inhibitor in the mixture.
  • corrosion inhibitor head groups may include amino-alkyl imidazolines, hydroxyl-alkyl imidazolines, imidazolinium and derivatives, pyridine and derivatives, pyridinium and derivatives, hexahydropyrimidines, amines and derivatives; quatemized amine and derivatives; and cyclic amine and derivatives, and the like.
  • Corrosion inhibitors in accordance with the present disclosure may also incorporate head group structures having functional groups containing oxygen atoms, including hydroxyl, ether, ester, and carboxylic acid groups.
  • kinetic and thermodynamic corrosion inhibitors in a mixture may have the same or different polar heterocyclic head group.
  • corrosion inhibitors may have a chemical structure according to general imidazoline structure (I), where Rl is a C2 to C4 carbon chain, which may include one or more hydroxyl, amine, or halogen groups; R2 is a C2 to C14 saturated or unsaturated hydrocarbon radical for kinetic inhibitors, and a C15 to C40 saturated or unsaturated hydrocarbon radical for thermodynamic inhibitors; and n is an integer between 1 and 4.
  • Rl is a C2 to C4 carbon chain, which may include one or more hydroxyl, amine, or halogen groups
  • R2 is a C2 to C14 saturated or unsaturated hydrocarbon radical for kinetic inhibitors, and a C15 to C40 saturated or unsaturated hydrocarbon radical for thermodynamic inhibitors
  • n is an integer between 1 and 4.
  • heterocyclic diamine corrosion inhibitors may be prepared from an annulation reaction by an alkyl diamine component and an aldehyde, carboxylic acid, or acid chloride component.
  • the alkyl diamine component may be of the general formula (II), where n is an integer between 3 and 6, and R4 and R5 are independently H or a C2-C40 saturated or unsaturated hydrocarbon radical such an alkyl, alkenyl, alkynyl, and the like.
  • the alkyl diamine component used to generate the imidazoline structure (I) may be an N-substituted diamine having a straight chain or branched alkyl or alkenyl substituent, including, for example, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n- and iso-nonyl, n- and iso-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n- hexadecyl, n-octadecyl, oleyl, linoleyl, linolenyl, and the like.
  • Aldehyde components reacted with the alkyl diamine may include one or more aldehydes that include, for example formaldehyde and C1-C30 saturated or unsaturated, aromatic or non-aromatic hydrocarbon radicals such as 2-hydroxynapthaldehyde, 7- phenyl-2,4,6-heptatrienal, crotonaldehyde, 2-hexenal, 2-heptenal, 2-octenal, 2-nonenal, 2- decenal, 2-undecenal, 2-dodecenal, 2,4-hexadienal, 2,4-heptadienal, 2,4-octadienal, 2,4- nonadienal, 2,4-decadienal, 2,4-undecadienal, 2,4-dodecadienal, 2,6-dodecadienal, citral, l-formyl-[2-(2-methylvinyl)]-2 -n-oct
  • Aldehyde components in accordance with the present disclosure may also include heteroaromatic substituted aldehydes such as pyridine-2-carboxaldehyde, pyridine-4- carboxaldehyde, alkylpyridinium aldehyde derivatives, furfuraldehydes, and the like.
  • aldehydes may include aldoses and other reducing sugars of any stereochemistry that include glyceraldehydes, pentoses, hexoses, and the like.
  • the aldehyde component may be generated from an aldehyde precursor such as paraformaldehyde, acetal, and the like.
  • a carboxylic acid component may be a C2-C30 saturated or unsaturated acid or fatty acid such as lauric acid, myristic acid, palmitic acid, and the like.
  • a carboxylic acid component may include natural mixtures of fatty acids and derivatives thereof that may contain various distributions of chain lengths. With particular respect to FIG. 1, a histogram is presented showing distributions of carbon chain numbers in samples of natural fatty acid mixtures including tall oil fatty acids, coconut oils, palm oil, palm kernel oil, and tallow oils. While a selection of potential fatty acid mixtures are shown, it is envisioned that any natural or synthetic blend of fatty acids may be used.
  • the carboxylic acid component may also include dimerized C2-C30 carboxylic acids such as dioleyl, dilinoleyl, dilinolenyl, and the like, including mixtures thereof.
  • corrosion inhibitors may be imidazoline, imidazoline with amino-alkyl side-chains and amino-alkyl-amino-alkyl side chains, imidazoline with hydroxy-alkyl side-chain, and mixtures of imidazolines, mono-amido amines, bis-amido amines, and amido-imidazolines.
  • Imidazoline-based corrosion inhibitors may be produced by a reaction of fatty acids with polyamines such as diethylenetriamine (DETA), hexamethylenetetramine (HMTA), N-(2- hydroxyethyl)ethylenediamine (HEED), and the like, in some embodiments, while bis- imidazolines may be prepared by a reaction of fatty acids with tetraethylenepentamine (TEPA) in some embodiments.
  • DETA diethylenetriamine
  • HMTA hexamethylenetetramine
  • HEED N-(2- hydroxyethyl)ethylenediamine
  • TEPA tetraethylenepentamine
  • corrosion inhibitors may have a general structure as shown in Formula (III), where R3 and R5 are independently selected from hydrogen, from C2-C14 saturated or unsaturated hydrocarbon radicals for kinetic inhibitors, and a C15-C30 saturated or unsaturated hydrocarbon radicals for thermodynamic inhibitors, with the proviso that at least one of R3 and R5 is not hydrogen; R4 is hydrogen or a Cl - C30 saturated or unsaturated, aromatic or non-aromatic hydrocarbon radical; and n is an integer between 1 and 4.
  • R3 and R5 are independently selected from hydrogen, from C2-C14 saturated or unsaturated hydrocarbon radicals for kinetic inhibitors, and a C15-C30 saturated or unsaturated hydrocarbon radicals for thermodynamic inhibitors, with the proviso that at least one of R3 and R5 is not hydrogen; R4 is hydrogen or a Cl - C30 saturated or unsaturated, aromatic or non-aromatic hydrocarbon radical; and n is an integer between 1 and 4.
  • inhibitors having the general structure (III) may be prepared from a reaction of an alkyl diamine component with an aldehyde, carboxylic acid, or acid chloride component, such as those described above, to form the heterocyclic product.
  • the alkyl diamine component may be of the general formula (IV), where n is an integer between 3 and 6, and R3 and R5 are independently selected from from hydrogen, from C2-C14 saturated or unsaturated hydrocarbon radicals for kinetic inhibitors, and a C15-C30 saturated or unsaturated hydrocarbon radicals for thermodynamic inhibitors, with the proviso that at least one of R3 and R5 is not hydrogen.
  • corrosion inhibitors may include bolaform inhibitors that include compounds having two (or more) terminal charged polar groups connected by a hydrophobic spacer.
  • Bolaform inhibitors may have the general structure (V), where R6 and R8 are polar species that may include quaternary amines, heterocycles, and other cyclic and acyclic structures substituted with charged substituents such as carboxylates, sulfonates, sulfonates, phosphates, ammonium groups, and the like; and R7 is a saturated or unsaturated, aromatic or nonaromatic alkyl or alkenyl spacer having a carbon number in the range of C2 to C30.
  • Examples of bolaform corrosion inhibitors may include bis-quinolinium derivatives such as phenyl bis-quinolinium dibromide, bis-3-picolinium derivatives such as N,N-dodecane-l,l2-diyl-bis-3-picolinium dibromide, and the like.
  • Blends of kinetic and thermodynamic corrosion inhibitors may include mixtures prepared by a number of general approaches that include: (1) varying the polar head group chemistry; (2) varying the chemistry of the hydrophobic tail or linker; (3) varying the type of inhibitor class based on film forming characteristics; and (4) mixtures of any of these approaches.
  • blends may include a kinetic inhibitor having a 5R p /5t of > 150 and a thermodynamic inhibitor having a 5R p /5t of ⁇ 150.
  • corrosion inhibitor blends may include a thermodynamic corrosion inhibitor that exhibits a long term R p that is > 4 times greater than the respective kinetic inhibitor in the blend.
  • blends may include mixtures of kinetic and thermodynamic corrosion inhibitors having a polar heterocyclic head group and a hydrophobic chain group, where the wherein the carbon number of the hydrophobic chain is in the range of C2 to C14 for the kinetic corrosion inhibitor, and C15 to C30 for the thermodynamic corrosion inhibitor.
  • corrosion inhibitor compositions may be prepared by blending the hydrophobic chain precursors for the kinetic and thermodynamic inhibitors and reacting the mixture with a common heterocyclic nucleus to generate the inhibitor blend in a single pot.
  • a corrosion inhibitor composition in which the kinetic and thermodynamic corrosion inhibitors have the general structure (I) may be prepared by blending fatty acids or derivatives of varying lengths, or by blending one or more sources of distributions of fatty acids and derivatives, such as natural oils including tall oil fatty acids, coconut oils, palm oil, palm kernel oil, tallow oils, and the like, which may then be reacted with polyamines such as diethylenetetramine (DETA) to form amino-ethyl imidazolines; or with hydroxylated polyamines such as N-(2-hydroxyethyl) ethylenediamine (HEED) to form the hydroxyl-ethyl imidazolines.
  • DETA diethylenetetramine
  • HEED hydroxylated polyamines
  • reaction product is a blend of reactants with shorter and longer hydrophobic chains.
  • the ratio of the resulting kinetic and thermodynamic inhibitors may also be adjusted by controlling the concentration of each reactant to account for different reactivities with DETA or HEED.
  • the kinetic and thermodynamic inhibitors may be synthesized separately and combined to form a corrosion inhibitor composition.
  • reactants for the kinetic and thermodynamic inhibitors may be combined to produce a corrosion inhibitor composition in a single pot.
  • a reactant mixture may include a bimodal carbon number distribution of reactant alkyl chains to produce a defined mixture of kinetic and thermodynamic inhibitors.
  • the bimodal distribution of carbon numbers in the hydrophobic chains of the blend may be prepared by blending reactants, such as fatty acids, rather than blending the products of two or more separate syntheses based on different reactant mixtures.
  • Corrosion inhibitor compositions in accordance with the present disclosure may contain a percent by weight (mol%) of kinetic and/or thermodynamic corrosion inhibitor that ranges from a lower limit selected from any of 5 wt%, 10 wt%, and 25 wt%, to an upper limit selected from any of 25 wt%, 50 wt%, and 75 wt%, where any lower limit may be paired with any upper limit.
  • mol% of kinetic and/or thermodynamic corrosion inhibitor that ranges from a lower limit selected from any of 5 wt%, 10 wt%, and 25 wt%, to an upper limit selected from any of 25 wt%, 50 wt%, and 75 wt%, where any lower limit may be paired with any upper limit.
  • corrosion inhibitor compositions may be added to a process stream at a dosage of 0.1 ppm to 10,000 ppm by weight, 1 to 1,000 ppm by weight, or 10 to 500 ppm by weight.
  • the corrosion inhibitors as individually disclosed herein may be used alone or in combination with other corrosion inhibitors to enhance a corrosion inhibition performance.
  • corrosion inhibitor compositions may applied to a metal surface at a working concentration that ranges from a lower limit selected from 0.05 mM, 0.10 mM, and 0.15 mM, to a upper limit selected from 0.2 mM, 0.5 mM, and 0.75 mM, where any lower limit may be combined with any upper limit.
  • corrosion inhibitor blends may have a molar ratio of kinetic corrosion inhibitor to thermodynamic inhibitor that is > 5:95, where the mol% of the kinetic corrosion inhibitor is > 5 mol% of the total moles of the corrosion inhibitor blend. In some embodiments, corrosion inhibitor blends may have a molar ratio of kinetic corrosion inhibitor to thermodynamic inhibitor that is > 10:90, where the mol% of the kinetic corrosion inhibitor is > 10 mol% of the total moles of the corrosion inhibitor blend.
  • molar ratio of kinetic corrosion inhibitor to thermodynamic inhibitor may be in a range of ratios having a lower limit selected from 2.5:97.5, 5:95, and 10:90, to an upper limit selected from 50:50, 60:40, and 75:25, where any lower limit may be combined with any upper limit.
  • corrosion inhibitor blends may have a molar ratio of kinetic corrosion inhibitor to thermodynamic inhibitor that is > 5:95, and the intial film formation rate of the inhibitor blend in the first two hours is >150 5R p /5t
  • the molar ration of the kinetic corrosion inhibitor may be more or less depending on the particular application and the film forming properties of the respective corrosion inhibitors.
  • corrosion inhibitor blends may contain one or more kinetic corrosion inhibitors and one or more thermodynamic corrosion inhibitors.
  • corrosion inhibitor compositions may include one or more synergists that increase the corrosion inhibition performance.
  • Synergists in accordance with the present disclosure may include mercaptoethanol, mercaptopropanol, l-mercapto-2-propanol, 2-mercaptobutanol, and the like; di- or poly-mercapto organic compounds such as di-mercapto derivatives of thiophene, pyrrole, furane, diazoles, and thiadiazoles; di- and tri-mercapto derivatives of pyridine, diazines, triazines benzimidazole, benzthiazole, thioglycolic acid, potassium iodide, and the like.
  • Corrosion inhibitor compositions in accordance with the present disclosure may contain a percent by weight (wt%) of synergist that ranges from a lower limit selected from any of 0.5 wt%, 1 wt%, and 1.5 wt%, to an upper limit selected from any of 2.5 wt%, 5 wt%, and 7.5 wt%, where any lower limit may be paired with any upper limit.
  • wt% percent by weight
  • Corrosion inhibitor compositions in accordance with the present disclosure may be formulated to contain one or more base fluids.
  • Base fluids may be oleaginous or aqueous and may include emulsions, foams, and other multiphase mixtures.
  • the aqueous fluid may be a brine, which may include seawater, aqueous solutions wherein the salt concentration is less than that of sea water, or aqueous solutions wherein the salt concentration is greater than that of sea water.
  • Salts that may be found in seawater include, but are not limited to, sodium, calcium, aluminum, magnesium, potassium, strontium, and lithium salts of chlorides, bromides, carbonates, iodides, chlorates, bromates, formates, nitrates, oxides, sulfates, silicates, phosphates and fluorides. Salts that may be incorporated in a brine include any one or more of those present in natural seawater or any other organic or inorganic dissolved salts.
  • Suitable oleaginous or oil-based fluids that may be used to formulate emulsions may include a natural or synthetic oil and in some embodiments, in some embodiments the oleaginous fluid may be selected from the group including diesel oil, mineral oil, a synthetic oil, such as hydrogenated and unhydrogenated olefins including polyalpha olefins, linear and branch olefins and the like, polydiorganosiloxanes, siloxanes, or organosiloxanes, esters of fatty acids, specifically straight chain, branched and cyclical alkyl ethers of fatty acids, mixtures thereof and similar compounds known to one of skill in the art; and mixtures thereof.
  • a synthetic oil such as hydrogenated and unhydrogenated olefins including polyalpha olefins, linear and branch olefins and the like, polydiorganosiloxanes, siloxanes, or organosiloxanes, esters of
  • base fluids may be include solvents considered as mutual solvents.
  • the use of the term“mutual solvent” includes its ordinary meaning as recognized by those skilled in the art, as having solubility in both aqueous and oleaginous fluids.
  • the mutual solvent may be substantially completely soluble in aqueous and oleaginous phases, while in other embodiments, a lesser degree of solubilization within a selected phase may be acceptable.
  • Such mutual solvents include alcohols, linear or branched such as isopropanol, methanol, glycerol, or glycols and glycol ethers such as 2- methoxyethanol, 2-propoxyethanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol dibutyl ether, diethylene glycol monoethyl ether, diethyleneglycol monomethyl ether, tripropylene butyl ether, dipropylene glycol butyl ether, diethylene glycol butyl ether, butylcarbitol, dipropylene glycol methyl ether, propylene glycol n-propyl ether, propylene glycol t-butyl ether, ether, and various esters, such as ethyl lactate, propylene carbonate, butylene
  • Base fluids in accordance with the present disclosure may be a percent by volume
  • (vol%) of a corrosion inhibitor composition in a range of 2.5 vol% to 30 vol% in some embodiments, and from 5 vol% to 25 vol% in other embodiments.
  • corrosion inhibitor compositions and blends are assayed for inhibiting performance at elevated temperatures. While the examples are described to demonstrate embodiments of the present disclosure in greater detail, the scope of the disclosure is not restricted by the following examples.
  • the kinetic and thermodynamic corrosion inhibitors in this study have an amino- ethyl imidazoline nucleus prepared by a reaction of diethylenetriamine (DETA) with lauric acid for the kinetic inhibitor, or a tall oil fatty acid mixture containing (29 % oleic acid (Cl8: l), 57 % linoleic acid (Cl8:2), 10 % palmitic (06:0) and about 2 % resin acids (mainly abietic acid) for the thermodynamic inhibitor.
  • DETA diethylenetriamine
  • lauric acid lauric acid
  • a tall oil fatty acid mixture containing (29 % oleic acid (Cl8: l), 57 % linoleic acid (Cl8:2), 10 % palmitic (06:0) and about 2 % resin acids (mainly abietic acid) for the thermodynamic inhibitor.
  • the corrosion inhibitors have the general structure (VI), where R for the kinetic inhibitor Al is a saturated Cl l alkyl, and the R for the thermodynamic inhibitor Bl is composed of partially unsaturated 07 chains, saturated 05 chains, and minor quantities of resin acid derivatives.
  • thermodynamic inhibitor Bl shows relatively slow inhibitor film formation kinetics and good resistance to corrosion (high Rp) during the period of 10 to 24 hours.
  • kinetic inhibitor Al shows rapid film formation kinetics, but exhibits a decrease in the resistance to corrosion during the period 2 to 12 hours and a lower resistance to corrosion relative to inhibitor Bl during the period 12 to 24 hours.
  • Blends of inhibitors Al and Bl exhibit intermediate curves depending on the molar ratio. In terms of achieving both rapid film formation kinetics and sustained high resistance to corrosion, the blend of 3: 1 Al:Bl appeared to be optimum under the selected conditions and concentrations.
  • FIG. 3 is proportional to total corrosion (total weight loss) during the period. Cumulative (l/Rp) values were calculated for each of the curves shown in FIG. 2. Again the result confirms that the blend of 3: 1 Al :Bl appeared to be optimum under the selected conditions and concentrations.
  • FIG. 4 a plot of the initial slope of the polarization resistance as a function of hydrocarbon chain length for a number of amino-ethyl imidazoline inhibitors of the general structure (VI) is shown. Samples were assayed by keeping the weight of the respective inhibitor constant at 50 mg/L (open squares), and by keeping the molar concentration constant at 143 pmol/L (black triangles). In the examples, it was observed that the rate of film formation for a kinetic inhibitor derived from lauric acid (where R is C11H23 ) is approximately 6 times faster than that of the thermodynamic inhibitors Bl derived from fatty acids having carbon chains containing 22 to 28 carbons. It is also noted that reproducibility appears to be better for longer chain lengths (C18 to C28) as compared to C12 and C14.
  • the head group chemistry for the inhibitors was modified to include a hydroxy-ethyl imidzaoline having the general structure (VII).
  • Samples assayed include kinetic inhibitor A2 in which R was C11H23 , prepared by reaction of N-(2-hy dr oxy ethyl) ethylenediamine (HEED) with lauric acid, and thermodynamic inhibitor B2 in which R is mainly composed of partially unsaturated C17 chains, saturated C15 chains, and minor quantities of polycyclic resin acids, prepared by reaction of N-(2 -hydroxy ethyl) ethylenediamine (HEED) with tall oil fatty acid.
  • kinetic inhibitor A2 in which R was C11H23 , prepared by reaction of N-(2-hy dr oxy ethyl) ethylenediamine (HEED) with lauric acid
  • thermodynamic inhibitor B2 in which R is mainly composed of partially unsaturated C17 chains, saturated C15 chains, and minor quantities of polycyclic resin acids, prepared by reaction of N-(2 -hydroxy ethyl) ethylenediamine (HEED) with tall oil fatty acid.
  • kinetic inhibitor A2 of this example shows more rapid film formation kinetics followed by rather variable behavior, but exhibit a decrease in the resistance during the periods 5 to 24 hours or 10 to 24 hours.
  • Blends of inhibitors A2 and B2 of this example show behavior that depends on the molar ratio A:B. In terms of achieving both rapid film formation kinetics and sustained high resistance to corrosion, the A2:B2 3: 1 blend appears optimum.
  • FIG. 6 the results are also shown in a bar chart depicting the cumulative inverse polarization resistance. Again, the cumulative inverse polarization resistance over 0 to 24 is directly proportional to total corrosion (total weight loss) during the period.
  • the performance of the A2:B2 3 : 1 blend is synergistic relative to the performance component A2 or B2 alone.
  • blends were prepared corrosion inhibitors having a hexahydropyrimidine nucleus having the general structure (VIII), where R is a saturated or unsaturated carbon chain and assayed for inhibition performance at l50°C.
  • Sample assays included kinetic inhibitor A3 in which R is C12H25, prepared from a reaction of formaldehyde with N-dodecyl propanediamine, and thermodynamic inhibitor B2 in which R is a mixture of saturated and partially unsaturated chains, including 14% stearic (Cl8:0), 47% oleic (Cl8: l), 3% linoleic (08:2 cis-9,l2), 1% linolenic (08:3 cis-9, 12, 15), 26% palmitic (06:0), 3% palmitoleic (06: 1), and 3% myristic (04:0), prepared from formaldehyde and N-tallow propanediamine.
  • kinetic inhibitor A3 in which R is C12H25, prepared from a reaction of formaldehyde with N-dodecyl propanediamine
  • thermodynamic inhibitor B2 in which R is a mixture of saturated and partially unsaturated chains, including 14% stearic
  • inhibitors A3 and B3 at high temperature were determined by weight loss analysis after immersion of 0018 C-steel test coupons in CCh-saturated 3 wt% NaCl brine at l50°C in an autoclave. With particular respect to FIG. 7, cumulative corrosion rates after 48 hours exposure is shown.
  • Samples tested include 500 ppm B3 (20% tallow hexahydropyrimidine) and 5 ppm of mercaptoethanol (2ME) in a brine base, which gave a final dosage of 100 ppm B3 and 5 ppm 2ME; 1,000 ppm B3 and 10 ppm 2ME in a brine base, which gave a final dosage of 200 ppm B3; and 10 ppm 2ME; 500 ppm formulation of A3 (20% Dodecyl hexahydropyrimidine) and 5 ppm 2ME, which provided a final dosages as follows of 100 ppm A3 and 5 ppm 2- mercaptoethanol; and a 500 ppm A3:B3 1 :3 blend with 5 ppm 2ME, which provided a final dosage of 75 ppm B3; 25 ppm A3; and 5 ppm 2ME-mercaptoethanol. As shown in FIG. 7, at half the dosage, the A3 alone is more efficient than B3, while further benefit is
  • Kinetic inhibitor A4 in this example was lauric ethlyamino imidazoline, while the thermodynamic inhibitor B4 is a mixture of inhibitors generated from the reaction of N-3-aminopropyl-N-benzyl-N,N-dimethylammonium bromide and tall oil fatty acid.
  • the inhibition performance of inhibitors A4 and B4 at high temperature was determined by the recorded polarization resistance R p as a function of time for a steel cylinders rotated at 2,000 rpm and immersed in CCh-saturated 3 wt% NaCl brine containing 0.143 mM concentration of a selected inhibitor or blend.
  • corrosion inhibitor compositions may be formulated to maximize adsorbtion on exposed metal surfaces, forming a protective inhibitor film that minimizes the exposure of the metal surface to a surrounding corrosive environment and decreasing the observed corrosion rate.
  • corrosion inhibitors may be added to a process stream that contacts a metal surface, covering and maintaining a protective film on the surface.
  • Process streams may include a number of components, including water, petroleum, petroleum products, hydrocarbons, and acidic species such as C0 2 and FhS, and salts such as NaCl.
  • Introduction of a corrosion inhibitor to a process stream may include injection of the corrosion inhibitor composition into a process stream at various intervals along a pipeline, well, or other conduit.
  • corrosion inhibitor compositions may effectively prevent and/or inhibit the formation of corrosion on metal materials and equipment, such as metal piping and flow lines used in various industrial applications.
  • corrosion inhibitor compositions may be added to a process stream by dosing at an effective concentration that may be estimated from similar applications in some embodiments, or determined by pre-treatment testing in some embodiments.
  • corrosion in inhibitor compositions in accordance with the present disclosure may be applied to metal surfaces by spraying, dipping, injection downhole, and the like.

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Abstract

L'invention concerne des compositions qui peuvent comprendre un mélange d'inhibiteurs de corrosion comprenant un inhibiteur de corrosion cinétique et un inhibiteur de corrosion thermodynamique, l'inhibiteur de corrosion cinétique ayant un taux de formation de film qui est au moins 1,5 fois supérieur au taux de formation de film respectif d'un inhibiteur de corrosion thermodynamique sur une surface métallique. Des procédés peuvent comprendre la mise en contact d'une surface métallique avec une composition d'inhibiteur de corrosion, la composition d'inhibiteur de corrosion comprenant un inhibiteur de corrosion cinétique et un inhibiteur de corrosion thermodynamique, l'inhibiteur de corrosion cinétique ayant un taux de formation de film qui est au moins 1,5 fois supérieur au taux de formation de film respectif d'un inhibiteur de corrosion thermodynamique sur une surface métallique.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112174892A (zh) * 2020-10-10 2021-01-05 宜兴金兑化工有限公司 一种石化生产中和剂的制备工艺

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2506925A1 (fr) * 2005-04-05 2006-10-05 Bj Services Company Methode de completion de puits au moyen d'inhibiteurs de formation d'hydrates de gaz
WO2015017385A2 (fr) * 2013-08-02 2015-02-05 Ecolab Usa Inc. Inhibiteurs de corrosion à base de disulfure organique

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2506925A1 (fr) * 2005-04-05 2006-10-05 Bj Services Company Methode de completion de puits au moyen d'inhibiteurs de formation d'hydrates de gaz
WO2015017385A2 (fr) * 2013-08-02 2015-02-05 Ecolab Usa Inc. Inhibiteurs de corrosion à base de disulfure organique

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112174892A (zh) * 2020-10-10 2021-01-05 宜兴金兑化工有限公司 一种石化生产中和剂的制备工艺

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