WO2017112721A1 - Inhibiteurs de corrosion et procédés associés pour leurs production et utilisation - Google Patents

Inhibiteurs de corrosion et procédés associés pour leurs production et utilisation Download PDF

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WO2017112721A1
WO2017112721A1 PCT/US2016/067908 US2016067908W WO2017112721A1 WO 2017112721 A1 WO2017112721 A1 WO 2017112721A1 US 2016067908 W US2016067908 W US 2016067908W WO 2017112721 A1 WO2017112721 A1 WO 2017112721A1
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alkyl
group
carbon atoms
halide
alkyl group
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PCT/US2016/067908
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Se Hye KIM
Joseph M. O'DAY
Thanikavelu Manimaran
Srinivasa S. GODAVARTHY
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Albemarle Corporation
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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
    • C23F11/04—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
    • C09K8/60—Compositions for stimulating production by acting on the underground formation
    • C09K8/62—Compositions for forming crevices or fractures
    • C09K8/72—Eroding chemicals, e.g. acids
    • C09K8/74—Eroding chemicals, e.g. acids combined with additives added for specific purposes
    • 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
    • C23F11/141—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—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 disclosure generally relates to quaternary ammonium halide compositions and related processes, and more particularly to quaternary ammonium halide compositions for inhibiting corrosion of a material in a concentrated acid solution, processes for preparing such compositions, and processes for using such compositions.
  • Acid treatments are frequently utilized in the oil and gas industry to improve a well's productivity or injectivity.
  • An acid treatment typically involves pumping acid through a pipeline into a wellbore or geologic formation.
  • Commonly used acid solutions can include organic acids (e.g., citric, formic, acetic acid, etc.) and mineral acids (e.g., hydrochloric or hydrofluoric acid).
  • organic acids e.g., citric, formic, acetic acid, etc.
  • mineral acids e.g., hydrochloric or hydrofluoric acid
  • acid solutions can cause corrosion of the metallic surface of the pipeline.
  • corrosion inhibitors are often used to protect the pipeline against corrosion.
  • a need remains in the art for a corrosion inhibitor capable of being efficiently adsorbed onto a metallic surface to form protective layer on the metallic surface.
  • a need also remains in the art for a more environmentally friendly corrosion inhibitor.
  • the present disclosure generally relates to one or more compositions suitable for inhibiting corrosion of a metal or metallic surface that is in contact with a concentrated acid solution and related processes for the production and use of the one or more compositions.
  • the composition includes one or more quaternary ammonium halides (I):
  • R 1 is an alkyl group having about 10 to about 20 carbon atoms
  • R 2 is an alkyl group having about 1 to about 4 carbon atoms
  • R 3 is an alkyl group having about 1 to about 4 carbon atoms
  • R 4 is an alpha alkyl omega aryl group
  • X 1 is Br.
  • the alpha alkyl omega aryl group may be substituted with a halide or an alkyl group, for example, an alpha alkyl omega benzyl group substituted with a halide or an alkyl group.
  • R 1 may be an alkyl group having about 14 to about 18 carbon atoms.
  • the quaternary ammonium halide ( ⁇ ) may be cetyldimethylbenzylammonium bromide, tetradecyldimethylbenzylammonium bromide, octadecyldimethylbenzylammonium bromide, a mixture of
  • alkyl dimethylbenzylammonium bromides wherein the number of carbon atoms comprising the alkyl group is from about 10 to about 18 carbon atoms, and/or mixtures thereof.
  • the composition includes one or more quaternary ammonium halides (II):
  • R 5 is an alkyl group having about 10 to about 20 carbon atoms
  • X 2 is Br, CI, or I.
  • R 5 may be an alkyl group having about 14 to about 18 carbon atoms.
  • the quaternary ammonium halide ( ⁇ ) may be, for example, 3-bromocetylpyridinium bromide.
  • an effective amount of the composition(s) described herein is/are added to the concentrated acid solution in contact with the metal or metallic surface.
  • the one or more quaternary ammonium halides is/are present in the composition in the range from about 5 ppm to about 50,000 ppm, more preferably in the range from about 10 ppm to about 100 ppm.
  • the concentrated acid solution may include hydrochloric acid (HQ), hydrofluoric acid (HF), sulfuric acid (H 2 S0 4 ), hydrobromic acid (HBr), and/or mixtures thereof.
  • the concentrated acid solution contains H 2 S0 4 , and H 2 S0 4 is present in a concentration in the range from about 3 wt.% to about 70 wt.%. It is still further contemplated that when the concentrated acid solution contains HQ, the HQ is present in a concentration in the range from about 3 wt.% to about 37 wt.%. It is still further contemplated that when the concentrated acid solution contains HBr, the HBr is present in a concentration in the range from about 3 wt.% to about 62 wt.%.
  • composition(s) described herein are produced by combining an aryl alcohol with an inorganic halide acid (e.g., HBr) to form an intermediate product mixture which is then combined with a tertiary amine thereby producing a mixture of one or more quaternary ammonium halides described herein.
  • an inorganic halide acid e.g., HBr
  • Figure 2 illustrates the test results shown in Table 2 for various quaternary ammonium halides used with A387-F11.
  • Figure 3 illustrates the test results shown in Table 2 for various quaternary ammonium halides used with A106 GB.
  • Figure 4 illustrates the test results shown in Table 3 for El and CE1 used with C1018.
  • Figure 5 illustrates the test results shown in Table 3 for El and CE1 used with N80.
  • Figure 6 illustrates the test results shown in Table 4 for El and CE1 used with C1018.
  • Figure 7 illustrates the test results shown in Table 4 for El and E4 used with C1018.
  • Figure 8 illustrates the test results shown in Table 6 for El, CE1, CE5, CE6 and CE7
  • compositions that inhibit the corrosion of a material such as a metal or metallic surface, processes for preparing such compositions, and processes of using of such compositions.
  • Such compositions are effective for inhibiting corrosion of a variety of materials including, but not limited to, carbon and alloy steels such as C1018, A387-F11, A106-GB, N80, and so forth.
  • compositions disclosed herein can be used in any system exposed to fluids (i.e., liquid, gas, slurry, mixtures thereof) that contain a corrosion agent, especially a metal corrosion agent, where improved corrosion inhibition is desired.
  • a corrosion agent especially a metal corrosion agent
  • the compositions disclosed herein can be used for inhibiting corrosion of any metal or metallic surface that is in contact with a concentrated acid solution.
  • the corrosion inhibitors of this disclosure are particularly well-suited for use in corrosive systems typically encountered in oil and gas operations and refinery operations, for example, an acid treatment in a pipeline for a wellbore or geologic formation.
  • HCl hydrochloric acid
  • HF hydrofluoric acid
  • mixtures of HCl and HF i.e., mud acid which is typically a blend of about 3-12 wt.% HCl and about 1-6 wt.% HF
  • sulfuric acid H 2 S0 4
  • hydrobromic acid HBr
  • acetic acid formic acid, other organic acids, and anhydrides.
  • Preferred concentrated acid solutions contain an acid selected from the group consisting of HCl, HF, H 2 S0 4
  • Preferred concentrated acid solutions include, but are not limited to, acid solutions containing H 2 S0 4 in a concentration in the range of from about 3 wt.% to about 70 wt.%, HCl in a concentration in the range from about 3 wt.% to about 37 wt.%, HBr in a concentration in the range from about 3 wt.% to about 62 wt.%, and mixtures of two or more of the foregoing acids.
  • a composition for inhibiting corrosion of a metal or metallic surface in a concentrated acid solution comprises at least one quaternary ammonium halide.
  • the quaternary ammonium halide comprises a quaternary ammonium cation and a counterion.
  • Providing the quaternary ammonium cation with a long chain alkyl group e.g., an alkyl group having about 10 to about 24 carbon atoms), can increase the hydrophobicity of the protective film.
  • alpha alkyl omega aryl group added to the quaternary ammonium cation can be substituted on the ortho, meta, and/ or para positions with a halide, preferably Br, CI, or I, and/ or an alkyl group, preferably a linear alkyl group having about 1 to about 6 carbon atoms.
  • the counterion has a charge sufficient to balance the positive charge on the quaternary ammonium cation.
  • the counterion provides the quaternary ammonium halide with increased nucleophilicity, polarizability, and hydrophobicity.
  • Suitable examples of counterions include, for example, at least one halide ion. Br (bromide), CI (chloride), or I (iodide) are preferred counterions because they are generally are more nucleophilic, polarizable and hydrophobic than, for example, F (fluoride). This is because nucleophilicity increases down the periodic table due to the increased polarizability and size of an atom, e.g., ( ⁇ > Br > CI > F).
  • a Br counterion forms more robust intermediate bridges on a metal surface, which gives rise to stronger bonding or adsorption with the metal, than a less poloarizable counterion such as F.
  • the combination of the substituted quaternary ammonium cation and a counterion provides a synergistic effect that improves the overall corrosion inhibition activity of the quaternary ammonium halide. Specifically, the adsorption of the counterion is higher on positively charged surfaces than on negatively charged surfaces while the adsorption of the substituted quaternary ammonium cation is higher on negatively charged surfaces. Thus, the combination of the cationic and anionic effect improves the overall adsorption of the quaternary ammonium halide with the surface of the material.
  • the composition comprises one or more quaternary ammonium halides selected from the group consisting Formula ( ⁇ ) and Formula ( ⁇ ).
  • a quaternary ammonium halide of Formula (I) can be represented by the following general formula:
  • R 1 is an alkyl group having about 10 to about 24 carbon atoms, preferably an alkyl group having about 10 to about 20 carbon atoms, more preferably an alkyl group having about 14 to about 18 carbon atoms
  • R 2 is an alkyl group having about 1 to about 6 carbon atoms, preferably about 1 to about 4 carbon atoms
  • R 3 is an alkyl group having about 1 to about 6 carbon atoms, preferably about 1 to about 6 carbon atoms
  • R 4 is an alpha alkyl omega aryl group, preferably an alpha alkyl omega aryl group substituted with a halide or an alkyl group, more preferably an alpha alkyl omega benzyl group substituted with a halide or an alkyl group
  • X is a counterion with a charge sufficient to balance the positive charge on the ammonium compound of Formula I.
  • Counterions include, halides, such as F, CI, Br, I, and combinations thereof; however, Br is a preferred counterion for at least the reasons discussed herein.
  • Non-limiting examples of quaternary ammonium halides of Formula ( ⁇ ) wherein R 4 is an alpha alkyl omega aryl group can be represented by the following general structure:
  • Y alkyl or halides
  • n 1-6
  • the N atom of the quaternary ammonium halide is bonded at the alpha position of the alkyl group (e.g. alkyl group containing about 1 to about 6 carbon atoms) and an aryl group is bonded to the omega position of alkyl chain.
  • the aryl group may be substituted with Y, wherein Y is an alkyl group or a halide.
  • the position of Y could be ortho-, meta-, and para- on the aryl ring.
  • Rep esentative quaternary ammonium halides of Formula ( ⁇ ) that can be used in the corrosion inhibiting composition(s) described herein include, but are not limited to, cetyldimethylbenzylammonium bromide, tetradecyldimethylbenzylammonium bromide, octadecyldimethylbenzylammonium bromide, and alkyl dimethylbenzylammonium bromide.
  • Alkyl dimethylbenzylammonium bromide comprises a mixture of
  • alkyldimethylbenzylammonium bromides where the number of carbon atoms comprising the alkyl group varies from about 10 to about 18 carbon atoms.
  • the mixture of alkyldimethylbenzylammonium bromides contains about 52 to about 63 wt.% of alkyl groups having about 14 carbon atoms, about 33 to about 52 wt.% of alkyl groups having about 16 carbon atoms, about 7 wt.% of alkyl groups having about 12 carbon atoms, about 7 wt.% of alkyl groups having about 18 carbon atoms, and about 2 wt.% of alkyl groups having about 10 carbon atoms.
  • Cetyldimethylbenzylammonium bromide, tetradecyldimethylbenzylammonium bromide, and alkyldimethylbenzylammonium bromide can be represented by the following structures respectively:
  • the quaternary ammonium halide of Formula ( ⁇ ) is selected from the group consisting of cetyldimethylbenzylammonium bromide,
  • a quaternary ammonium halide of Formula (IT) can be represented the following general formula:
  • variables in Formula (TT) represent the following: A is monocyclic or bicyclic heteroaromatic ring group substituted with a halide or alkyl group, preferably a halide; R 5 is an alkyl group having about 10 to about 24 carbon atoms, preferably an alkyl having about 10 to about 20 carbon atoms, more preferably an alkyl having about 14 to about 18 carbon atoms; and X 2 is a counterion with a charge sufficient to balance the positive charge on the parent compound of Formula (II).
  • Representative counterions include those discussed above with respect to Formula ( ⁇ ), with Br, CI, or I as preferred counterions for at least the reasons discussed above.
  • Representative quaternary ammonium halides of Formula ( ⁇ ) that can be used in corrosion inhibiting composition(s) described herein include, but are not limited to, 3- bromocetylpyridinium bromide and 2-methylcetylpyridinium bromide, which can be represented by following structures respectively:
  • the quaternary ammonium halide of Formula (II) is selected from the group consisting of 3-bromocetylpyridinium bromide, 2-methylcetylpyridinium bromide, and mixtures thereof.
  • A in quaternary ammonium halides of Formula (II )wherein A is a bicyclic ring, A can be, for example, quinoline or isoquinoline.
  • Such compounds can be represented by following structures:
  • R is an alkyl, halide or hydro xyl group.
  • quaternary ammonium halides of Formula (II) include:
  • an effective amount of the corrosion inhibiting composition(s) described herein is added to a concentrated acid solution in contact with a metal or metallic surface.
  • the one or more quaternary ammonium halides as described herein is/are generally present in the composition in an amount in the range of from about 5 ppm to about 50,000 ppm, more preferably about 10 ppm to about 400 ppm, most preferably about 10 ppm to about 100 ppm.
  • the composition can further comprise at least one solvent.
  • the composition containing the one or more quaternary ammonium halides is/are typically added to oil, water, and/ or gas fluids in the form of a solution or dispersion in a solvent.
  • Suitable solvents include, but are not limited to, alcohols, hydrocarbons, ketones, ethers, aromatics, amides, nitriles, sulfoxides, esters, aqueous systems, and combinations thereof.
  • the solvent can be water, isopropanol, methanol, ethanol, 2-ethylhexanol, heavy aromatic naphtha, toluene, ethylene glycol, ethylene glycol monobutyl ether (EGMBE), diethylene glycol monoethyl ether, or xylene.
  • EGMBE ethylene glycol monobutyl ether
  • Representative polar solvents suitable for formulation with the composition include water, brine, seawater, alcohols (including straight chain or branched aliphatic such as methanol, ethanol, propanol, isopropanol, butanol, 2- ethylhexanol, hexanol, octanol, decanol, 2-butoxyethanol, etc.), glycols and derivatives (ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, ethylene glycol monobutyl ether, etc.), ketones (cyclohexanone, diisobutylketone), N-methylpyrrolidinone (NMP), N,N- dimethylformamide, and so forth.
  • alcohols including straight chain or branched aliphatic such as methanol, ethanol, propanol, isopropanol, butanol, 2- ethylhexanol, hexanol, octanol,
  • non-polar solvents suitable for formulation with the composition include aliphatic hydrocarbons such as pentane, hexane, cyclohexane, methylcyclohexane, heptane, decane, dodecane, diesel, and so forth; aromatic hydrocarbons such as toluene, xylene, heavy aromatic naphtha; and fatty acid derivatives (acids, esters, amides), and so forth.
  • aliphatic hydrocarbons such as pentane, hexane, cyclohexane, methylcyclohexane, heptane, decane, dodecane, diesel, and so forth
  • aromatic hydrocarbons such as toluene, xylene, heavy aromatic naphtha
  • fatty acid derivatives ascids, esters, amides
  • the composition can further comprise additional components commonly used in acidizing fluids, for example, solvents as described above (e.g., alkyl alcohol and glycol), surfactants (i.e., dispersing agents), chelating/ sequestering agents, wetting agents, friction reducers, scale inhibitors, carbon dioxide control additives, paraffin control additives, oxygen control additives, salt inhibitors, iron control agents, non-emulsifiers, foaming agents, bactericides, hardening agents, solubility modifiers, defoamers, sulfide scavenger, anti- redeposition agents, clay stabilizer, or fluid loss control agents.
  • solvents as described above e.g., alkyl alcohol and glycol
  • surfactants i.e., dispersing agents
  • chelating/ sequestering agents i.e., dispersing agents
  • wetting agents e.g., friction reducers, scale inhibitors
  • carbon dioxide control additives e.g., paraffin control additives
  • compositions can be applied to a fluid or gas in any selected concentration depending on the type of corrosive system. That is, each corrosive system can have its own requirements, and the effective amount of a composition to sufficiently reduce the rate of corrosion can vary with the system in which it is used.
  • the composition(s) of this disclosure are added to the concentrated acid solution in contact with the metal or metallic surface to provide an effective treating dose.
  • the one or more quaternary ammonium halides in the composition(s) is/are present in the corrosive system in a concentration in the range from about 5 to about 50,000 ppm, more preferably about 10 to about 400 ppm, most preferably about 10 to about 100 ppm.
  • compositions of the present disclosure exhibited similar or in some cases superior corrosion inhibiting activity than the other corrosion inhibiting composition even when present in lower concentrations, for example, El vs. CE1 as shown in Figs. 4-6.
  • Utilizing a smaller dose of a corrosion inhibitor that offers a similar or better corrosion protection performance is of particular advantage because it is environmentally friendly (i.e., less corrosion inhibitor is required) in addition to gaining a benefit of cost reduction. It also reduces the effort to remove the corrosion inhibitor after its usage, thus it makes recycling of acid solutions easier.
  • a fluid treated with a composition of the invention can be at any selected
  • the fluid e.g., acidic aqueous solution
  • the fluid can be at a temperature in the range from about 25 °C to about 100 °C, more preferably about 40 °C to about 90 °C, most preferably about 60 °C to about 80 °C.
  • composition may be introduced to the concentrated acid solution in contact with the metal or metallic surface in accordance with techniques well-known to those skilled in the art that ensure dispersal of the composition through the fluid.
  • the composition may be introduced to the concentrated acid solution in contact with the metal or metallic surface in accordance with techniques well-known to those skilled in the art that ensure dispersal of the composition through the fluid.
  • the metal or metallic surface in accordance with techniques well-known to those skilled in the art that ensure dispersal of the composition through the fluid.
  • composition(s) can be added at a point in a flow line upstream from the point at which corrosion prevention is desired.
  • the composition(s) can be injected or pumped into a flow line using mechanical equipment such as chemical injection pumps, piping tees, injection fittings, atomizers, quills, and so forth.
  • the composition(s) of the invention can be introduced with or without one or more of the solvents and/ or additional components described above depending upon the application and requirements.
  • the one or more quaternary ammonium halides described herein are generally prepared using reactions in an aqueous system starting from an alcohol such as an aryl or alkyl alcohol, preferably an aryl alcohol.
  • the alcohol is combined with an inorganic halide acid, such as a concentrated aqueous strong acid, to form an intermediate halide product mixture comprising one or more halides (e.g., alkyl halide or aryl halide), preferably an aryl halide.
  • the intermediate halide product mixture is combined an amine, preferably a tertiary amine thereby producing a mixture of one or more quaternary ammonium halides as described above.
  • Suitable alcohols include, but are not limited to, having alkyl substituents with about 1 to about 10 carbon atoms such as a linear or branched alkyl, benzyl, cycloalkyl, alkyl ether, and alkyl ester.
  • Suitable inorganic halide acids include, but are not limited to, hydrogen halides such as HI (hydrogen iodide), HBr (hydrogen bromide), HC1 (hydrogen chloride), and HF (hydrogen fluoride), and combinations thereof, with aqueous HBr as a preferred inorganic halide acid.
  • the concentration of the inorganic halide acid may vary depending upon the reaction conditions.
  • HBr acid concentration of greater than about 33 wt.% is preferred and more preferably 62 wt%.
  • the amine is preferably a tertiary amine having alkyl or aryl substituents with about 1 to about 24 carbon atoms.
  • suitable alkyl substituents include, but are not limited to, cycloalky, heterocyclic, hydroxyl alkyl, hydroxyl cycloalkyl, alkyl ether, alkyl ester, alkyl thioester, alkenyl, and alkynyl.
  • Aryl substituents can be a monocyclic, bicyclic, or tricyclic aromatic, for example, phenyl, benzyl, and heteroaryl (e.g. pyridine, imidazole).
  • one substituent of the tertiary amine is preferably an alkyl having about 12 to about 20 carbon atoms.
  • the one or more quaternary ammonium halides prepared in accordance with this disclosure may be more environmentally friendly than other processes well-known by those of ordinary skill in the art. For example, little to no hazardous byproduct is produced and no organic solvent is required throughout the entire process. Only water and nontoxic inorganic salt with desired quaternary ammonium halide can typically be produced, which may offer the reduced cost of hazardous waste treatment.
  • the entire process can be conducted in water as a solvent, and if necessary, polar solvents such as alcohols (e.g., ethanol) may be used as a solvent.
  • the one or more quaternary ammonium halides are preferably prepared as described above, it should be appreciated that the compositions described herein can be prepared in accordance with other techniques well-known to those skilled in the art.
  • PBr 3 phosphorous tribromide
  • this reaction generally requires a low temperature (below 0 °C) and usually provides a lower yield, and can generate phosphorous acid as a byproduct, which should be removed for the next reaction.
  • Corrosion studies were conducted either based on the following procedures: (1) ASTM G31 - 72 (Reapproved 2004): Standard Practice for Laboratory Immersion Corrosion Testing of Metals; or (2) the test protocol described below.
  • the selected test metal coupons were added to the inhibited acid solutions and these solutions were placed in an oven at the desired elevated temperature. The coupons remained in the oven for the test duration, typically in the range from one hour to 28 days depending on the test conditions. Metal coupons were carefully weighed before and after the tests. After the test, coupons were removed from the reaction vessels, cleaned and weighed to obtain their weight loss. The corrosion value was given in mils per year (mpy).
  • corrosion inhibitor compositions containing quaternary ammonium halides such as cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, cetylpyridinium bromide, and cetylbenzyldimethylammonium chloride were also tested following the above described procedures.
  • propargyl alcohol, butyne diol, and triethanolamine were tested as comparative examples. These compounds were selected as representative examples of different categories of corrosion inhibitors.
  • Propargyl alcohol and butyne diol are examples of acetylenic alcohol and acetylenic diol, which showed excellent performance in many applications such as oilfield acidification and steel acid pickling.
  • Triethanolamine has been also known as one of the commonly used amine type corrosion inhibitors.
  • the quaternary ammonium halides and few other commonly used corrosion inhibitors utilized in the tests are summarized in Table 1 below.
  • the results of the tests using quaternary ammonium halides are set forth in Table 2 below, and also illustrated in the appended figures.
  • Test Conditions for Table 2 400 ppm of corrosion inhibitor loading; 3 wt.% HCl, 60 °C; and 28 days.
  • compositions of the present disclosure (E1-E3) generally exhibit superior corrosion inhibiting activity than the compositions of the comparative examples (CE1-CE3).
  • El exhibits superior corrosion resistance compared to CE1 and CE2
  • E2 exhibits superior corrosion resistance compared to CE3.
  • the superior performance of compounds of this disclosure is surprising and believed, at least in part, to be due to functionalizing the quaternary ammonium cation, which can provide increased electron density and stability to the compound thereby improving adhesion with a metal or metallic surface of a material and resulting in the formation of an excellent protective film on the surface of the material.
  • compositions of the present disclosure exhibited similar or in some cases superior corrosion inhibiting activity than the compositions of the comparative examples even when present in lower concentrations, for example, El vs. CE1 as shown in Figs. 4-6.
  • 1-12 M (mol/L) concentrations of HCl was tested in the presence of El, and compared to test results for CEl under the same test conditions.
  • Mild carbon steel (C1018) and oilfield pipeline metal alloy (NT 80) were tested under the sample condition (500 ppm of corrosion inhibitor loading, 60 °C, and 3-24 hours of metal coupon immersion time depending on the acid concentration).
  • El consistently showed the superior corrosion results under all HCl concentrations
  • Figure 6 illustrates the increasing trend of corrosion rates as concentrations of corrosion inhibitor CE1 decreased from 1000 ppm to 50 ppm while El showed consistent corrosion rates under all corrosion inhibitor concentrations. It is worth emphasizing that even with 10 times higher corrosion inhibitor loading of CE1, El performed better under the same corrosive environment. For example, a concentration of 1000 ppm of CE1 exhibited a corrosion rate of 519 mpy whereas the corrosion rate was 91 mpy for a concentration 50 ppm of El.
  • ADMA-16, ADMA-14, and ADMA-1416 are N, N-dimethyl-l-hexadecaneamine, N, N- dimethyl-l-tetradecaneamine, and N, N-dimethyl-l-alkylamine (mixture of C 10 -C 18 ), respectively.
  • Table 4 and Figure 7 showed that E4 followed the similar pattern as El with about 10 % increase of corrosion rates as compared to El.
  • El and CE5 displayed similar corrosion rate at concentration of about 1,000 ppm and the corrosion rate of El was better with corrosion inhibitor loading lower than about 1,000 ppm. El showed constant or substantially constant performance even at about 10 ppm loading while CE5 slowly lost its efficiency as corrosion inhibitor concentration decreased.
  • Propargyl alcohol is a commonly accepted standard corrosion inhibitor for acidification, but it produces toxic vapors during the acidification process and it is difficult to store/handle due to its highly flammable character. Unlike propargyl alcohol, El generates no toxic byproducts during the acidification process and it offers high thermal/chemical stability.
  • CE6 requires about 5000 times more CI loading.
  • CE7 could not achieve the such high performance even with about 5000 times more CI loading.
  • Quaternary ammonium halides were prepared by the following synthetic procedures. Alkyl alcohol was heated with concentrated aqueous HBr to generate alkyl bromide. A tertiary amine was further reacted with alkyl bromide to obtain the desired quaternary ammonium halides. The entire process was conducted in water as solvent, substantially only H 2 0 was generated as a byproduct, and unreacted reagent can be easily recycled for the next batch.
  • Alkylbenzyldimethylammonium bromide was prepared as described below. A round- bottom flask equipped with a condenser was charged with benzyl alcohol (1 eq) and aqueous HBr solution (1-1.5 eq). This mixture was agitated (temperature may vary from room temperature (e.g., about 22 °C to about 150 °C) to generate benzyl bromide until completing the conversion. Benzyl bromide was further reacted with alkyldimethylamine and then the reaction mixture was heated in water (0-80 wt. %) at about 60-150 °C for about 1-6 hours. The resulting mixture was cooled down to about 0-25 °C until white precipitate formed. The white solid was collected by filtration and then dried.
  • a concentrated aqueous HBr (33-62% in water, if necessary anhydrous gas HBr is used) was added to benzyl alcohol without additional solvent to generate benzyl bromide.
  • Alkyldimethyl amine was reacted with benzyl bromide to obtain desired ammonium bromide with or without additional water.
  • the reaction to prepare benzyl bromide may be stirred at room temperature (e.g., about 22 °C), or heated at any temperature below about 150 °C. When anhydrous HBr gas was used, external heat may not be needed due to the exothermic nature of reaction.
  • the period of time may be from about 0.5 to about 6 hours. This reaction may last for any period of time until it is determined that a sufficient amount of benzyl bromide has formed.
  • the ratio between each reactant to synthesize benzyl bromide may vary based on the reaction conditions. In order to maximize the conversion of benzyl bromide, excess amount (1-2 eq.) of HBr, highly concentrated aqueous HBr (62% or higher), or anhydrous HBr (gas) may be required, which could be easily collected after reaction by a simple extraction of aqueous layer and recycled for the next batch. If necessary, benzyl bromide could be purified by distillation to remove water after the reaction and this purified benzyl bromide was further reacted with alkyldimethyl amine in water.
  • alkyldimethyl amine compounds used for this process are
  • ALBEMARLE® commercial products with different alkyl chain length include more than 98 wt.% pure desired alkyldimethyl amines.
  • ADMA-1416 contains 52-63 wt.% of C14 ( ,N- dimethyl l-tetradecaneamme, CAS-No: 112-75-4), 33-52 wt.% of C16 ( ⁇ , ⁇ -dimethyl 1- hexadecaneamine, CAS-No: 112-69-6),7 wt.% of C12 ( ⁇ , ⁇ -dimethyl 1-dodecaneamine, CAS- No: 112-18-5), higher than 7 wt.% of C18 ( , ⁇ -dimethyl 1-octadecaneamine, CAS-No: 124- 28-7), and 2 wt.% of CIO ( , ⁇ -dimethyl -1-decaneamme, CAS-No: 1120-24-7).
  • Alkyldimethyl amine was reacted with benzyl bromide with a vigorous agitation at elevated temperature, e.g. a temperature in the range from about 22 °C to about 150 °C.
  • elevated temperature e.g. a temperature in the range from about 22 °C to about 150 °C.
  • the period of time may be from about 0.5 hour to about 6 hours. This reaction may last for any period of time until it is determined that a sufficient amount of quaternary ammonium bromide has formed.
  • ADMA-16 ,N-dimethylcetylamme, 611.8 g, 2.27 mol, 1.0 eq
  • benzyl bromide 30 % (-200 g)of total volume of ADMA-16 ( ,N-dimethylcetylamme, 611.8 g, 2.27 mol, 1.0 eq) was slowly added to benzyl bromide with a vigorous agitation.
  • This mixture was heated for 15 more minutes and then rest of ADMA-16 (—412 g) and 0.8 L of water were co-feeded.
  • This resulting mixture was continuously heated at 90°C for 1 hour with vigorous agitation and cooled down to room temperature ( ⁇ 23°C) until white solid formed.
  • the resulting solid was filtered and dried to obtain the white solid product.
  • Quantitative Structure— Activity Relationship (QSAR) computational modeling was conducted to evaluate the toxicity of quaternary ammonium bromide by using octanol-water partition coefficient (Log P) and bioconcentration factor (BCF).
  • Log P value is used as a measure of molecular hydrophobicity and the value higher than 5 and smaller than 8 was considered as highly bioaccumulative.
  • introduction of benzyl group increases the hydrophobicity of quaternary ammonium bromide, however, El was not still considered as highly bioaccumulative.
  • Bromo-substituted quaternary ammonium, E2 also showed the very small increases of the Log P value.
  • BCF shows a steady-state distribution of chemical between aquatic organism and water.
  • the term "about” modifying the quantity of an ingredient in the compositions of the invention or employed in the methods of the invention refers to variation in the numerical quantity that can occur, for example, through typical measuring and liquid handling procedures used for making concentrates or use solutions in the real world; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of the ingredients employed to make the compositions or carry out the methods; and the like.
  • the term “about” also encompasses amounts that differ due to different equilibrium conditions for a composition resulting from a particular initial mixture. Whether or not modified by the term "about”, the claims include equivalents to the quantities.

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Abstract

La présente invention concerne des compositions inhibitrices de corrosion et des procédés associés pour leurs production et utilisation. La composition comprend un ou plusieurs halogénures d'ammonium quaternaire. Les un ou plusieurs halogénures d'ammonium quaternaire comprennent un cation d'ammonium quaternaire et un contre-ion. Le contre-ion présente une charge suffisante pour équilibrer la charge positive sur le cation d'ammonium quaternaire.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10894910B2 (en) 2018-10-31 2021-01-19 Saudi Arabian Oil Company Additives for oil and gas drilling and production

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2617771A (en) * 1946-09-27 1952-11-11 Hooker Electrochemical Co Corrosion retarder
US4402759A (en) * 1979-09-17 1983-09-06 Solvay & Cie. (Societe Anonyme) Process for inhibiting the corrosion of a metal installation in contact with an acid bath
US5096618A (en) * 1987-02-12 1992-03-17 Dowell Schlumberger Incorporated Process and composition for inhibiting high-temperature iron and steel corrosion
US6521028B1 (en) * 1996-11-04 2003-02-18 Hydrochem Industrial Services, Inc. Low hazard corrosion inhibitors and cleaning solutions using quaternary ammonium salts
US20080308770A1 (en) * 2007-06-14 2008-12-18 Laxmikant Tiwari Mono and bis-ester derivatives of pyridinium and quinolinium compounds as environmentally friendly corrosion inhibitors
US20090057616A1 (en) * 2007-08-31 2009-03-05 Clariant International Ltd. Corrosion inhibitors containing cationic surfactants
WO2015168430A1 (fr) * 2014-05-01 2015-11-05 Agienic, Inc. Compositions servant à la protection contre la corrosion

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2617771A (en) * 1946-09-27 1952-11-11 Hooker Electrochemical Co Corrosion retarder
US4402759A (en) * 1979-09-17 1983-09-06 Solvay & Cie. (Societe Anonyme) Process for inhibiting the corrosion of a metal installation in contact with an acid bath
US5096618A (en) * 1987-02-12 1992-03-17 Dowell Schlumberger Incorporated Process and composition for inhibiting high-temperature iron and steel corrosion
US6521028B1 (en) * 1996-11-04 2003-02-18 Hydrochem Industrial Services, Inc. Low hazard corrosion inhibitors and cleaning solutions using quaternary ammonium salts
US20080308770A1 (en) * 2007-06-14 2008-12-18 Laxmikant Tiwari Mono and bis-ester derivatives of pyridinium and quinolinium compounds as environmentally friendly corrosion inhibitors
US20090057616A1 (en) * 2007-08-31 2009-03-05 Clariant International Ltd. Corrosion inhibitors containing cationic surfactants
WO2015168430A1 (fr) * 2014-05-01 2015-11-05 Agienic, Inc. Compositions servant à la protection contre la corrosion

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10894910B2 (en) 2018-10-31 2021-01-19 Saudi Arabian Oil Company Additives for oil and gas drilling and production

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