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WO2021058251A1 - Inhibiteurs de corrosion pour fluides de traitement souterrain acides - Google Patents

Inhibiteurs de corrosion pour fluides de traitement souterrain acides Download PDF

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Publication number
WO2021058251A1
WO2021058251A1 PCT/EP2020/074579 EP2020074579W WO2021058251A1 WO 2021058251 A1 WO2021058251 A1 WO 2021058251A1 EP 2020074579 W EP2020074579 W EP 2020074579W WO 2021058251 A1 WO2021058251 A1 WO 2021058251A1
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branched
linear
hydrogen
group
corrosion inhibitor
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Inventor
Daniele CROSTA
Lorenzo GIARDINI
Luigi Merli
Giovanni Floridi
Giuseppe Li Bassi
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Lamberti SpA
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Lamberti SpA
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Classifications

    • 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
    • C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid 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
    • C23F11/12—Oxygen-containing compounds
    • C23F11/122—Alcohols; Aldehydes; Ketones
    • 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 present invention relates to corrosion inhibitors for use in aqueous acidic fluids for the treatment of subterranean formations.
  • the invention relates also to aqueous acidic subterranean treatment fluids comprising between 0.1 and 4.0 g/100 ml of said corrosion inhibitors, based on the total fluid volume.
  • Acidic fluids are present in a multitude of operations in the oil and gas industry.
  • acidic fluids are often used as a treating fluid in wells penetrating subterranean formations.
  • Such acidic treatment fluids may be used in, for example, clean-up operations or stimulation operations for oil and gas wells.
  • Acidic stimulation operations may use these treatment fluids in hydraulic fracturing and acidizing treatments.
  • acidizing treatments aqueous acidic fluids are introduced into the subterranean formation under pressure so that the acid permeates into the pore spaces of the formation. The acid reacts with acid- soluble materials contained in the formation, which causes an increase in the size of the pore and the spaces and enhances the permeability of the formation.
  • one or more fractures are produced in the formation and the acidic fluid is introduced into the fracture to etch channels in the fracture surface.
  • the acid also enlarges the pore spaces in the fracture surface and in the formation.
  • metal surfaces in piping, tubing, heat exchangers, reactors etc. are exposed to these acidic fluids.
  • One problem is that the acids, in addition to increasing the permeability of a hydrocarbon bearing formation, may also cause harmful corrosion and deterioration of the metal equipment. Anything made of metal in contact with the acid may be subject to such excessive corrosion.
  • the high temperatures occurring in some subterranean formations further increase the problem. For these reasons, it is mandatory to add one or more efficient corrosion inhibitors, for example organic corrosion inhibitors, to the acidic subterranean treatment fluids.
  • organic inhibitors adsorb on the metal surface and influence the rate of corrosion by one or more of the following mechanisms: (i) by forming a physical barrier film which restricts the diffusion of species to/from the metal surface, (ii) by blocking anodic and/or cathodic reaction sites directly, (iii) by interacting with corrosion reaction intermediates adsorbed on the surface and (iv) by influencing the electrical double layer that forms at the metal/solution interface.
  • a large number of organic corrosion inhibitors have been developed and used for application to various systems depending on the formation treated, the kind of metal that is susceptible to corrosion, the kind of corrosion encountered, and the environmental conditions to which the medium is exposed.
  • Exemplary organic corrosion inhibitors for acidic subterranean treatment fluids may include: acetylenic alcohols; Mannich condensation products; unsaturated carbonyl compounds; unsaturated ether compounds; formamide; formates; iodides; terpenes; aromatic hydrocarbons; cinnamaldehyde and cinnamaldehyde derivatives; fluorinated surfactants; quaternary derivatives of heterocyclic nitrogen bases; quaternary derivatives of halomethylated aromatic compounds; and combinations thereof.
  • the treatment fluids and additives thereof exhibit particularly low levels of toxicity towards marine microbial life forms also since these microorganisms enter into the food chain of larger life forms and are critical to maintain a stable ecosystem.
  • compositions comprising 1,3,5-hexahydrotriazines (hexahydro-s-triazine) or 1,3-oxazolidines or 1,3-oxazolidines and cinnamaldehyde or derivatives thereof, when added to aqueous acidic subterranean treatment fluids act as a corrosion inhibitor surprisingly effective in minimizing damaging of the metal equipment with performances higherthan the performances of the single ingredients dosed in the same amount. At the same time, they do not affect the ecotoxicological profile of said acidic subterranean treatment fluids.
  • cinnamaldehyde and derivatives thereof have been disclosed in US 3,589,860, US 4,734,259, US 5,854,180, US 6,117,364 and US 2008/0227668.
  • 1,3-oxazolidine and bisoxazolidine and derivatives thereof have been disclosed in US 4,518,519, US 5,328,635, WO 9,608,308, WO 95/14528 and US 2016/176828.
  • compositions comprising hexahydro-s-triazine or 1,3-oxazolidine or bisoxazolidine and cinnamaldehyde or derivatives thereof as corrosion inhibitors for aqueous acidic subterranean treatment fluids has never been described before.
  • the percent weight/volume is expressed in gram/100ml, equivalent to 3.5 pound/barrel.
  • an aqueous corrosion inhibitor comprising: a) from 0.5 to 35 % by weight (wt%), preferably from 1 to 25 wt%, of a heterocyclic compound chosen among hexahydro-s-triazines, 1,3- oxazolidines, bisoxazolidines and mixtures thereof; b) from 0.5 to 50 wt%, preferably from 1 to 35 wt%, of a cinnamaldehyde; c) from 0 to 45 wt%, preferably from 1 to 35 wt%, of an acetophenone.
  • aqueous acidic subterranean treatment fluid comprising from 0.1 to 4.0 g/100ml of said aqueous corrosion inhibitor based the total fluid volume.
  • the present invention provides a method of reducing or inhibiting corrosion of metal equipment in treating subterranean formations that comprises: providing said aqueous acidic subterranean treatment fluid, introducing the aqueous acidic fluid into at least a portion of a subterranean formation and allowing the fluid to interact with the subterranean formation, while the corrosion of the metal equipment is effectively reduced or inhibited.
  • the aqueous corrosion inhibitor according to the present invention comprises ingredients giving it an environmental classification of at least "Yellow” or a better rating according to the Norwegian classification scheme or a classification "Gold" within the CEFAS registration scheme.
  • the aqueous corrosion inhibitor comprises from 3 to 75 wt%, preferably from 5 to 50 wt%, more preferably from 8 to 40 wt%, of water.
  • the sum of ingredients a) and b) represents more than 5 wt%, preferably more than 10 wt%, more preferably more than 20 wt%, of the aqueous corrosion inhibitor of the invention.
  • hexahydro-s-triazine includes the compounds of formula I:
  • Ri, R2 and R3 may be identical or different and are, independently of each other, hydrogen, a linear or branched C1-C0 alkyl group optionally substituted with one or more units chosen from hydroxy (—OH) and alkoxy (—OR'), where R' is a linear or branched C1-C0 alkyl group; or Ri, R2 and R3 are a substituted or unsubstituted cycloalkyl or aryl group;
  • Ra, R b and R c may be identical or different and are, independently of each other, hydrogen, a linear or branched C1-C0 alkyl group, a substituted or unsubstituted cycloalkyl or aryl group.
  • linear or branched C1-C0 alkyl groups are methyl, ethyl, n-propyl, iso propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl, tert-pentyl, and linear or branched hexyl groups.
  • Methyl, ethyl, n-propyl, and iso-propyl groups are preferred.
  • substituted linear or branched C1-C0 alkyl groups are 2- hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-methoxyethyl, 3- methoxypropyl groups and the like.
  • Suitable substituted or unsubstituted aryl groups are phenyl, naphthyl, tolyl, xylyl groups.
  • R a , Rb and R c are identical. More preferably, they are all hydrogen or a phenyl group.
  • Ri, R2 and R3 are identical.
  • Ri, R2 and R3 are identical and are chosen in the group consisting of methyl, ethyl, propyl, hydroxyethyl and 3-methoxypropyl groups. Most preferably, Ri, R2 and R3 are all hydroxyethyl groups.
  • the compounds of formula I are known in the art. Many of them are commercially available; the others can be prepared following known procedures described in the art. Specific examples of commercial hexahydro-s-triazine of formula I, which are particularly suitable for the realization of the present invention, are 1,3,5- trimethyl hexahydro-s-triazine, 1,3,5-tris(isopropyl) hexahydro-s-triazine, 1,3,5- tris(hydroxyethyl) hexahydro-s-triazine, 2,4,6-tris(phenyl)-1,3,5-tris(2- hydroxyethyl)hexahydro-s-triazine and 1,3,5-tri(methoxypropyl) hexahydro-s- triazine.
  • 1,3-Oxazolidine is a five-membered ring compound consisting of three carbons, a nitrogen, and an oxygen.
  • the oxygen and the nitrogen are in the 1 and 3 positions, respectively.
  • 1,3-oxazolidine includes the compounds of formula II:
  • R4 and R5 can be, independently of each other, hydrogen, a linear or branched C1-C0 alkyl or hydroxyalkyl group, such as methyl, ethyl or hydroxyethyl; a substituted or unsubstituted cycloalkyl or aryl group, such as phenyl;
  • R0, R7 and Re can be, independently of each other, hydrogen, a linear or branched C1-C0 alkyl or an hydroxyalkyl group, such as methyl, ethyl or hydroxyethyl;
  • R9 can be hydrogen, a linear or branched C1-C0 alkyl group, such as methyl or ethyl; and
  • R10 can be hydrogen, a linear or branched C1-C0 alkyl or hydroxyalkyl group, such as methyl, ethyl or hydroxyethyl, a substituted or unsubstituted cycloalkyl or aryl
  • 1,3-oxazolidines examples include oxazolidines such as N-(2-hydroxyethyl) 1,3-oxazolidine, 4,4-dimethyl 1,3- oxazolidine and 3,4,4-trimethyl 1,3-oxazolidine. 4,4-dimethyl 1,3-oxazolidine is the preferred 1,3-oxazolidine.
  • 1,3-Oxazolidines are cyclic condensation products of b-amino alcohols and aldehydes or ketone and can be obtained with methods known in the art.
  • bisoxazolidine includes the compounds of formula III: wherein: Rii and R12 are, independently of each other, hydrogen, a linear or branched Ci-
  • Rn and R12 are, independently of each other, hydrogen, a linear or branched C1-C3 alkyl group or a phenyl group. In the most preferred embodiment, Rn and R12 are methyl groups and the bisazolidine is 3,3'- methylenebis-[5-methyl oxazolidine].
  • the bisoxazolidines of the invention can be obtained by reaction of b-amino alcohols containing from about 3 to about 10 carbon atoms with formaldehyde in an appropriate molar ratio.
  • cinnamaldehydes suitable for the realization of the present invention include cinnamaldehyde, dicinnamaldehyde, p-hydroxy cinnamaldehyde, p-methyl cinnamaldehyde, p-ethyl cinnamaldehyde, p- methoxy cinnamaldehyde, p-dimethylamino cinnamaldehyde, p-diethylamino cinnamaldehyde, p-nitro cinnamaldehyde, o-nitro cinnamaldehyde, o-allyloxy cinnamaldehyde, p-thiocyano cinnamaldehyde, p-
  • acetophenones examples include acetophenone, p-methoxy acetophenone and p-chloroacetophenone.
  • the corrosion inhibitor of the invention can also comprise one or more surfactants for dispersing the active ingredients in the aqueous acidic subterranean treatment fluid, in an amount ranging from 2 to 45 wt%, preferably from 5 to 35 wt%.
  • Suitable surfactants include, but are not limited to, anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and zwitterionic surfactants.
  • Anionic surfactants include alkoxylated alkylphenol and arylphenol sulfates, alkoxylated alkylphenol and arylphenol phosphates, olefin sulfonates, paraffin sulfonates, fatty alcohol sulphates and phosphates, alkoxylated fatty alcohol sulphates and phosphates, fatty acids and alkoxylated fatty acids, anionic esters of alkyl polyglycosides, mono and dialkyl sulfosuccinates and sulfosuccinamates.
  • Nonionic surfactants include alkoxylated fatty alcohols, alkoxylated alkylphenols and arylphenols, block copolymers of ethylene, propylene and butylene oxides, alkyl dimethyl amine oxides, alkyl amidopropyl dimethyl amine oxides, alkyl polyglycosides, alkoxylated glycerides, sorbitan esters and alkoxylated sorbitan esters, alkoxylated fatty amines and alkoxylated fatty acids.
  • Cationic surfactants include alkyl trimethyl quaternary ammonium salts, alkyl dimethyl benzyl quaternary ammonium salts, dialkyl dimethyl quaternary ammonium salts, and imidazolinium salts.
  • amphoteric and zwitterionic surfactants examples include betaines and sultaines, amphoacetates and amphodiacetates, alkyl amphopropionates and amphodipropionates, and alkyliminodiproprionates.
  • Cationic, amphoteric and non-ionic surfactants are preferred.
  • Preferred cationic surfactants are alkyl trimethyl quaternary ammonium salts and dialkyl dimethyl quaternary ammonium salts, such as cetyl trimethyl ammonium chloride and didecyl dimethyl ammonium chloride.
  • Preferred amphoteric surfactants are sultaines, such as lauryl hydroxysultaine.
  • Preferred non-ionic surfactants are alkoxylated fatty acids, alkoxylated fatty alcohols and alkoxylated fatty amines.
  • the aqueous corrosion inhibitor of the invention comprises: a) from 0.5 to 35 wt%, preferably from 1 to 25 wt% of a heterocyclic compound chosen among hexahydro-s-triazines, 1,3-oxazolidines, bisoxazolidines and mixtures thereof; b) from 0.5 to 50 wt%, preferably from 1 to 35 wt% of a cinnamaldehyde; c) from 1 to 35 wt% of an acetophenone; d) from 2 to 45 wt%, preferably from 5 to 35 wt%, of one or more cationic, amphoteric and non-ionic surfactants or mixture thereof.
  • the corrosion inhibitor of the invention can also comprise an acid, such as phosphoric acid or an organic acid or mixtures thereof.
  • organic acids are formic, acetic acid, propionic acid, and lactic acid.
  • the concentration of the acid can be in the range from 5 to 35 wt%, preferably from 15 to 30 wt%.
  • Another ingredient that can be included in the corrosion inhibitor of the invention is a mutual solvent.
  • mutual solvent we mean a solvent having a polar, water- soluble group attached to a nonpolar hydrocarbon chain.
  • Mutual solvents are additives, used in oil field and well applications that are soluble in oil, water and acid-based treatment fluids, wherein they are routinely used for removing heavy hydrocarbon deposits, controlling the wettability of the contact surfaces before, during or after a treatment, and preventing or breaking emulsions.
  • the mutual solvent may be substantially completely soluble in each phase, while in other embodiments, a low degree of solubilization may be preferable.
  • Ci-C 6 alcohols such as methanol, ethanol, 2-propanol, n-butanol and iso- butanol
  • glycols and polyglycols such as monoethylene glycol, monopropylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, hexylene glycol, and higher glycols
  • glycol ethers such as 2-methoxyethanol, 2- propoxyethanol, 2-ethoxyethanol, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethyleneglycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, triethylene glycol monobutyl ether and the like; polyols, such as
  • a mutual solvent of the type described above When a mutual solvent of the type described above is included in a corrosion inhibitor of this invention, it is generally present in an amount in the range of from 1% to 40% by weight of the composition.
  • the metals that can be protected from corrosion by the aqueous corrosion inhibitor of the present invention include carbon-steel which can contain manganese or chromium in amount greater than 0.7 wt %, for examples N80, L80, J55, P110, C95, QT800, QT900, HS80, HS90, and the like; or corrosion resistant alloys (CRA) containing stainless steel and a variable chromium content, ranging from 1 to 40 wt %, for example 13Cr-L80, 13Cr-L110, 25Cr alloys, and the like.
  • Suitable metals also include non-ferrous metals such as aluminum, zinc, nickel, and copper, and their alloys.
  • the amount of inhibitor to be employed in the aqueous acidic subterranean treatment fluid varies depending on such factors as the temperature of the formation to be treated, the kind of acid to be inhibited, the kind of metal to be protected and the like.
  • the aqueous acidic subterranean treatment fluid comprises from 0.15 to 3.0 g/100ml, more preferably from 0.2 to 1.5 g/100ml, of corrosion inhibitor of the invention based the total fluid volume.
  • the aqueous treatment fluid comprises an acid.
  • the acid may be included in an amount in the range of from 0.001 to 45 wt% of the total fluid weight.
  • the acid is added in an amount in the range of from 1 to 36 wt%, more preferably from 9 to 27 wt%, of the total fluid weight.
  • the acid may be inorganic, organic and any combination thereof.
  • suitable inorganic acid include, but are not limited to, hydrochloric acid, hydrofluoric acid, phosphonic acids, nitric acid, sulfuric acid, phosphoric acid, potassium dihydrogenphosphate, sodium dihydrogenphosphate, acid sodium hexametaphosphate, acid potassium hexametaphosphate, acid sodium pyrophosphate, acid potassium pyrophosphate, sulfamic acid and mixtures thereof.
  • Suitable organic acid include acetic acid, carbonic acid, p-toluene sulfonic acid, propionic acid, oxalic acid, malonic acid, succinic acid, adipic acid, fumaric acid, maleic acid, hydroxy acids, such as glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, and combinations thereof.
  • Preferred acids are hydrochloric acid and hydrofluoric acid.
  • the aqueous acidic subterranean treatment fluid may comprise additionally organic solvents, which are miscible with the acid aqueous fluid.
  • additional solvents are the mutual solvents described above.
  • the proportion of water is at least 80% by weight, preferably 90% by weight and particularly preferably at least 95% by weight, based in each case on the total amount of all solvents used.
  • the aqueous acidic fluid of the present invention may optionally comprises from 0.1 to 4 g/100ml of one or more surfactants.
  • Surfactants may aid in the dispersibility of the various ingredients and/or may assist in the coating of the corrosion inhibitor on at least a portion of the metal surfaces to be protected. Suitable surfactants are those mentioned before.
  • the aqueous acidic subterranean treatment fluid of the invention can also comprise a corrosion inhibition intensifier.
  • a corrosion inhibition intensifier is a chemical compound that itself does not inhibit corrosion, but enhances the effectiveness of a corrosion inhibitor compound.
  • suitable corrosion inhibitor intensifiers are sources of iodide ions or cuprous ions, such as potassium iodide or cuprous chloride, acid soluble antimony or bismuth compounds and formic acid.
  • the corrosion inhibition intensifier is preferably in a concentration comprised between 0.1 and 20 g/100ml, more preferably between 0.1 and 10 g/100ml, based on the total volume of the subterranean treatment fluid.
  • the aqueous acidic subterranean treatment fluid of the invention can be emulsified with a non-aqueous fluid.
  • the emulsion can be of the oil-in-water type or water-in-oil type.
  • the treatment fluid of the present invention may further comprise additional ingredient commonly used in subterranean treatment fluids, such as, for example, rheology modifiers, salts, scale inhibitors, clay stabilizers, friction reducers, gases, foaming agents, solubilizers, wetting agents, diverting agents and the like. Combinations of these ingredients can be used as well.
  • additional ingredient commonly used in subterranean treatment fluids such as, for example, rheology modifiers, salts, scale inhibitors, clay stabilizers, friction reducers, gases, foaming agents, solubilizers, wetting agents, diverting agents and the like. Combinations of these ingredients can be used as well.
  • aqueous acidic subterranean treatment fluids of the invention can be prepared by conventional methods.
  • aqueous acidic subterranean treatment fluids can be used in methods of reducing or inhibiting corrosion of metal equipment in treating subterranean formations.
  • treatment of subterranean formations we mean any activity directed to extraction of gas or oil materials from a subterranean formation, for example, drilling, stimulation, hydraulic fracturing, clean-up, acidizing, completion, remedial treatment, abandonment, and the like.
  • the methods of reducing or inhibiting corrosion of metal equipment may be used in near well bore clean-out operations, wherein the aqueous acidic fluids of the invention may be circulated in the subterranean formations, thereby suspending or solubilizing particulates residing in the formations.
  • the treatment fluids be then may recovered out of the formations, carrying the suspended or solubilized particulates with it.
  • the methods of the invention may be used in operations of hydraulic fracturing, wherein the aqueous acidic fluids may be pumped into a well bore that penetrates a subterranean formation at a sufficient hydraulic pressure to create or enhance fractures in the subterranean formations, increasing the permeation of oil and gas through the formations.
  • Phenyl MEA Triazine obtained from the condensation of monoethanol amine and benzaldehyde, 89 wt% active substance in water;
  • Cinnamaldehyde Cinnamaldehyde
  • Rolfat OL/14/L ethoxylated oleic acid, commercialized by Lamberti S.p.A.
  • Rolfor HT/20 ethoxylated fatty alcohol, commercialized by Lamberti S.p.A.
  • TA 015 ethoxylated tallow amine, commercialized by Lamberti S.p.A.
  • • Mackam CBS 50G Lauryl Hydroxy Sultaine, 50 wt% active substance commercialized by Solvay SA;
  • Tables 1-3 report the amounts of ingredients (in grams) used for the preparation of the corrosion inhibitors of Examples 1-15.
  • the corrosion inhibition performances of the aqueous inhibitors of Examples 1-15 were determined under conditions that simulate the conditions existing in oil and gas well.
  • N80 metal coupons having a surface area of 37 cm 2 and weighing about 40 g were washed with water and soap, then rinsed with acetone and dried in oven at 50 °C for 1 hour. After the treatment, the coupons were weighed on an analytical balance.
  • An acid solution containing 15 wt% hydrochloric acid in deionized water was prepared. About 100 ml of this solution were transferred into a 150 mL jar; 0,6 g of corrosion inhibitor were added to the solution and the mixture was homogenized by shaking the capped jar. A metal coupon was suspended into the acid fluid using a Teflon® string. Each jar was filled with 10 ml_ of mineral oil and capped loosely. The jars were then maintained for 24 hours at 60 °C in an oil bath. The coupons were then removed from the jars, washed with water and soap, rinsed with acetone, dried and reweighed. The weight loss (WL) expressed as the difference between the weight of the metal coupon before and after the test was calculated.
  • WL weight loss
  • % Protection 100 * (WLb - WU)/WL b
  • WLb weight loss (mg ) in the blank test
  • WLi weight loss (mg) in the inhibitor test.
  • Tables 4-6 report the results of the tests.
  • the corrosion inhibitors of this invention show performances sharply higher than the comparative corrosion inhibitors containing the single ingredients.

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Abstract

L'invention concerne des inhibiteurs de corrosion destinés à être utilisés dans des fluides acides pour le traitement de formations souterraines et des fluides de traitement souterrain acides comprenant entre 0,1 et 4,0 g/100 ml desdits inhibiteurs de corrosion, sur la base du volume total de fluide.
PCT/EP2020/074579 2019-09-23 2020-09-03 Inhibiteurs de corrosion pour fluides de traitement souterrain acides Ceased WO2021058251A1 (fr)

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IT102019000017051A IT201900017051A1 (it) 2019-09-23 2019-09-23 Inibitori di corrosione per fluidi acidi per trattamenti sotterranei

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