CA2880361A1 - Corrosion inhibition composition for pipelines, process of elaboration and synthesis - Google Patents
Corrosion inhibition composition for pipelines, process of elaboration and synthesis Download PDFInfo
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- CA2880361A1 CA2880361A1 CA2880361A CA2880361A CA2880361A1 CA 2880361 A1 CA2880361 A1 CA 2880361A1 CA 2880361 A CA2880361 A CA 2880361A CA 2880361 A CA2880361 A CA 2880361A CA 2880361 A1 CA2880361 A1 CA 2880361A1
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
- F17D—PIPE-LINE SYSTEMS; PIPE-LINES
- F17D3/00—Arrangements for supervising or controlling working operations
- F17D3/12—Arrangements for supervising or controlling working operations for injecting a composition into the line
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Abstract
Corrosion inhibitors are provided for pipelines that transport crude oil and/or congenital water containing high salt concentrations, or for metal surfaces in contact with same. The corrosion inhibiting composition is a mixture of at least two different compounds in an organic solvent, providing a synergic effect. Said compounds are selected from the group consisting of imidazoles and benzotriazoles.
The mixture of at least two different compounds can also include at least one of each of ionic liquids, imidazoles and benzotriazoles.
The mixture of at least two different compounds can also include at least one of each of ionic liquids, imidazoles and benzotriazoles.
Description
CORROSION INHIBITION COMPOSITION FOR PIPELINES. PROCESS
OF ELABORATION AND SYNTHESIS
SPECIFICATION
TECHNICAL FIELD OF THE INVENTION
The current invention is related to the synthesis of basic compounds, the preparation of compositions and its application as corrosion inhibitors for pipelines that transport, besides of crude oil, associated congenital water containing high salt concentrations; the inhibitors are basically constituted by compounds of molecular structure families such as: imidazoles, benzotriazoles and ionic liquids; said formulations can include 2 or more components of each family and can use as alcohol solvents, xylene, toluene or mixtures thereof.
The inhibitors object of the current invention control the corrosion of metallic surfaces of the pipelines containing concentrations of congenital water from 0.2 up to 40% by weight, salt concentration between 10,000 and 70,000 ppm and concentration of hydrogen sulfide between 0 and 600 ppm, by means of the synergic effect between 2 or more components of the same family, or 2 or more different molecular structure families; this synergy is derived from its interactions with the metallic surface, among themselves or with the corrosive medium itself due to its chemical, physical and transportation properties, based on the length of the involved chain,
OF ELABORATION AND SYNTHESIS
SPECIFICATION
TECHNICAL FIELD OF THE INVENTION
The current invention is related to the synthesis of basic compounds, the preparation of compositions and its application as corrosion inhibitors for pipelines that transport, besides of crude oil, associated congenital water containing high salt concentrations; the inhibitors are basically constituted by compounds of molecular structure families such as: imidazoles, benzotriazoles and ionic liquids; said formulations can include 2 or more components of each family and can use as alcohol solvents, xylene, toluene or mixtures thereof.
The inhibitors object of the current invention control the corrosion of metallic surfaces of the pipelines containing concentrations of congenital water from 0.2 up to 40% by weight, salt concentration between 10,000 and 70,000 ppm and concentration of hydrogen sulfide between 0 and 600 ppm, by means of the synergic effect between 2 or more components of the same family, or 2 or more different molecular structure families; this synergy is derived from its interactions with the metallic surface, among themselves or with the corrosive medium itself due to its chemical, physical and transportation properties, based on the length of the involved chain,
2 that improves corrosion control achieving the simultaneous decrease of dosing of formulations. Whereas, the ternary formulations use a component of each one of the three families or 2 components of the same family and a third component belonging to the second family of molecules. In all cases, the formulations can include solvents as xylene, methanol and toluene, or a mixture of two or three of them.
The application of these compounds and formulations is focused, but not limited to its use as corrosion inhibitors in typical transportation environments of crude oil and petroleum industry generally.
BACKGROUND OF THE INVENTION
Corrosion inhibitors are compounds or formulations of chemical compounds wherein the active part blocks or modifies the electronic transfer process, responsible of the corrosion phenomena, between the metallic surface and the surrounding medium. In the petroleum industry, its use is generalized to control metal corrosion in a wide variety of mediums and conditions. Independently of the system, the interaction between the active component and the metallic surface plays a determining role in its development and consequently in the corrosion control; said interaction depends on the chemical properties of the active compound depending on its molecular structure, on physical and chemical properties of the metal and its own interaction with the surrounding medium; furthermore, of the operation conditions such as system pressure, temperature and hydrodynamics.
The application of these compounds and formulations is focused, but not limited to its use as corrosion inhibitors in typical transportation environments of crude oil and petroleum industry generally.
BACKGROUND OF THE INVENTION
Corrosion inhibitors are compounds or formulations of chemical compounds wherein the active part blocks or modifies the electronic transfer process, responsible of the corrosion phenomena, between the metallic surface and the surrounding medium. In the petroleum industry, its use is generalized to control metal corrosion in a wide variety of mediums and conditions. Independently of the system, the interaction between the active component and the metallic surface plays a determining role in its development and consequently in the corrosion control; said interaction depends on the chemical properties of the active compound depending on its molecular structure, on physical and chemical properties of the metal and its own interaction with the surrounding medium; furthermore, of the operation conditions such as system pressure, temperature and hydrodynamics.
3 In the particular case of pipes for the transportation of crude oil (pipelines), the control of the internal corrosion is complicated mainly by the frequent variations present in the type of the transported crude, as well as in the water, salts and dissolved gases contents;
nevertheless, the use of inhibitors is still the more profitable alternative to face it.
Among the main chemical families that have been used to inhibit corrosion in pipelines are nitrogenous compounds such as ammonium quaternary salts, amines, amides and including aminoacids; particularly the use of fat imidazolines and fat amines as corrosion inhibitors in the petroleum industry is well known.
Generally, it is accepted that these compounds work upon absorption forming a protecting film over the metallic surface; nevertheless, independent of the inhibitor used, these also have limitations.
In the literature that mentions the use of corrosion inhibitors with specific application for hydrocarbons transport, are the following international patents:
Patent US 7,057,050 B2 refers to the preparation of novel corrosion inhibitors imidazoline base and its use to inhibit corrosion in metallic flow lines. According to the patent, the inhibitors are a series of new corrosion inhibitors based on imidazoline base substituted with acrylates, of the following formula:
R, N N
nevertheless, the use of inhibitors is still the more profitable alternative to face it.
Among the main chemical families that have been used to inhibit corrosion in pipelines are nitrogenous compounds such as ammonium quaternary salts, amines, amides and including aminoacids; particularly the use of fat imidazolines and fat amines as corrosion inhibitors in the petroleum industry is well known.
Generally, it is accepted that these compounds work upon absorption forming a protecting film over the metallic surface; nevertheless, independent of the inhibitor used, these also have limitations.
In the literature that mentions the use of corrosion inhibitors with specific application for hydrocarbons transport, are the following international patents:
Patent US 7,057,050 B2 refers to the preparation of novel corrosion inhibitors imidazoline base and its use to inhibit corrosion in metallic flow lines. According to the patent, the inhibitors are a series of new corrosion inhibitors based on imidazoline base substituted with acrylates, of the following formula:
R, N N
4 Wherein R1 is an alkyl radical having from 2 to 8 carbon atoms;
R2 is a radical derived from a fatty acid, and R3 is a radical derived from an unsaturated acid.
Patent US 7,160,507 B2 relates to an additive and a method of corrosion inhibition on devices used for the recovery, transportation and processing of crude oil; the inhibitor comprises an alkoxylated quaternary compound of the formula:
where R1 and R2 are independently groups of the formula ¨(B)-(0-A)n-O-CO-R5 or -(A-0)n-(C)-CO-O-R5; R3 is C1- to C30- alkyl or C2 to C30- alkenyl; R4 is an organic radical with 1 to 100 atoms optionally containing heteroatoms; R5 is an alkyl or an alkenyl; n is a number from 1 to 20; A is an alkylene group; B is an alkylene group, C is a C1 -to C30-alkylene and X is an anion.
In patent application US 0084612 Al, a method for inhibiting corrosion in metallic surfaces used in manufacture, transportation, storage and separation of crude oil and gas is described; the method comprises adding the fluid a sufficient quantity of a synergist, when H2S is present in the fluid, or no synergist when H2S is present in the fluid and a composition comprising the following formula and salts thereof:
x-<,µ
,====
Wherein R1 and R3, CnH2n+i wherein n= 0 to 12; benzyl; or H. R2 is a C1 to C22 alkyl. X- is a halogen or a carboxylate and is only present when R1 and R3 are present. Y is (CH2), with n=1 to 8 and wherein R3 and R1 cannot be hydrogen at the same time.
R2 is a radical derived from a fatty acid, and R3 is a radical derived from an unsaturated acid.
Patent US 7,160,507 B2 relates to an additive and a method of corrosion inhibition on devices used for the recovery, transportation and processing of crude oil; the inhibitor comprises an alkoxylated quaternary compound of the formula:
where R1 and R2 are independently groups of the formula ¨(B)-(0-A)n-O-CO-R5 or -(A-0)n-(C)-CO-O-R5; R3 is C1- to C30- alkyl or C2 to C30- alkenyl; R4 is an organic radical with 1 to 100 atoms optionally containing heteroatoms; R5 is an alkyl or an alkenyl; n is a number from 1 to 20; A is an alkylene group; B is an alkylene group, C is a C1 -to C30-alkylene and X is an anion.
In patent application US 0084612 Al, a method for inhibiting corrosion in metallic surfaces used in manufacture, transportation, storage and separation of crude oil and gas is described; the method comprises adding the fluid a sufficient quantity of a synergist, when H2S is present in the fluid, or no synergist when H2S is present in the fluid and a composition comprising the following formula and salts thereof:
x-<,µ
,====
Wherein R1 and R3, CnH2n+i wherein n= 0 to 12; benzyl; or H. R2 is a C1 to C22 alkyl. X- is a halogen or a carboxylate and is only present when R1 and R3 are present. Y is (CH2), with n=1 to 8 and wherein R3 and R1 cannot be hydrogen at the same time.
5 Another structure mentioned in this patent application is:
Ri, N/0 \ R2 N.1/-wherein R1 and R2 are similar to the above structure and is CnH2n+1 wherein n = 0 is a C1 to C22 alkyl. X- = Cl, Br or I.
Patent application WO 157234 A2 relates to novel quaternary-nitrogen compounds in its structure and formulations used by these compounds that are useful as corrosion inhibitors in the gas and petroleum industry. The quaternary nitrogen-containing corrosion inhibitors have the following formula:
Ar -L---Y
X
Ar Wherein: is an aromatic, nitrogen-containing ring of 5 to 14 atoms, optionally containing an additional N, 0 or S ring atom in the additional N ring or can be substituted with one or more alkyl, alkenyl, aryl, arylalkyl, cycloalkyl, amine, aminoalkyl, alkoxy, hydroxyalkyl or cyano groups, or a mixture thereof; Y is a group of
Ri, N/0 \ R2 N.1/-wherein R1 and R2 are similar to the above structure and is CnH2n+1 wherein n = 0 is a C1 to C22 alkyl. X- = Cl, Br or I.
Patent application WO 157234 A2 relates to novel quaternary-nitrogen compounds in its structure and formulations used by these compounds that are useful as corrosion inhibitors in the gas and petroleum industry. The quaternary nitrogen-containing corrosion inhibitors have the following formula:
Ar -L---Y
X
Ar Wherein: is an aromatic, nitrogen-containing ring of 5 to 14 atoms, optionally containing an additional N, 0 or S ring atom in the additional N ring or can be substituted with one or more alkyl, alkenyl, aryl, arylalkyl, cycloalkyl, amine, aminoalkyl, alkoxy, hydroxyalkyl or cyano groups, or a mixture thereof; Y is a group of
6 formula ¨0C(0)R1; L is an C1-C10 alkyl, C2-C20 alkenyl of the formula ¨CH2CH(0R2) CH2-; R1 is C8-C20 alkenyl; R2 is H or ¨C(0)R1; R3 and R4 are independently selected from H, alkyl, alkenyl, amino, aminoalkyl, alkoxy, hydroxyalkyl or cyano; and X is Br, Cl or I.
Patent application WO 091429 Al relates to corrosion inhibition in ferrous and non-ferrous metals in aqueous-based environments by the use of formulations that use at least two mercaptan compounds of the following formulae:
p nX
q m SH SH
wherein X is C, N, 0 or S; R1, R2, R3 y R4 are independently H
or methyl; n and m are independently integers from 1 to 5 and p and q are independently integers from 1 to 4.
0H2) /12C
m wherein m is an integer from 3 to 4; and
Patent application WO 091429 Al relates to corrosion inhibition in ferrous and non-ferrous metals in aqueous-based environments by the use of formulations that use at least two mercaptan compounds of the following formulae:
p nX
q m SH SH
wherein X is C, N, 0 or S; R1, R2, R3 y R4 are independently H
or methyl; n and m are independently integers from 1 to 5 and p and q are independently integers from 1 to 4.
0H2) /12C
m wherein m is an integer from 3 to 4; and
7.7S)/"N(,, I-1)m HS
wherein m is an integer from 1 to 4; and n = 4 ¨ m.
On its part, patent application WO 128313 A2 relates to a corrosion inhibitor for use in the oil and gas exploration, recovery and processing industries consisting of a quaternary ammonium compound of the formula:
0-4E-0 -}¨X
I 4.
Z +0-E O-D¨N-R
I r wherein R is C1-6 alkyl, C2_6 alkenyl, aryl, aralkyl; X, Y and Z
are each independently H or RICO- group, provided that at least one of X, Y, Z is RICO- where R1 is a C5-23 alkyl or alkenyl containing 0, 1, 2, or 3 double bounds; D is C2_6 alkylene; E is C2_4 alkylene; p, q and r are independently integers from 0 to 20, with the proviso that p+q+r = 3 to 20; and A is an anion.
Other patent applications related to corrosion inhibitors with application in crude oil transportation are patent application WO
000895 Al that refers to a polymeric product obtained by the reaction between alkoxylated fat amine and a dicarboxylic acid derivative, whereas patent application WO 028542 Al refers to the use of polyamine polyester compounds and polyquaternary polyester ammonium as corrosion inhibitors in the transportation of crude oil and in the oil and gas wells.
wherein m is an integer from 1 to 4; and n = 4 ¨ m.
On its part, patent application WO 128313 A2 relates to a corrosion inhibitor for use in the oil and gas exploration, recovery and processing industries consisting of a quaternary ammonium compound of the formula:
0-4E-0 -}¨X
I 4.
Z +0-E O-D¨N-R
I r wherein R is C1-6 alkyl, C2_6 alkenyl, aryl, aralkyl; X, Y and Z
are each independently H or RICO- group, provided that at least one of X, Y, Z is RICO- where R1 is a C5-23 alkyl or alkenyl containing 0, 1, 2, or 3 double bounds; D is C2_6 alkylene; E is C2_4 alkylene; p, q and r are independently integers from 0 to 20, with the proviso that p+q+r = 3 to 20; and A is an anion.
Other patent applications related to corrosion inhibitors with application in crude oil transportation are patent application WO
000895 Al that refers to a polymeric product obtained by the reaction between alkoxylated fat amine and a dicarboxylic acid derivative, whereas patent application WO 028542 Al refers to the use of polyamine polyester compounds and polyquaternary polyester ammonium as corrosion inhibitors in the transportation of crude oil and in the oil and gas wells.
8 BRIEF SUMMARY OF THE DRAWINGS OF THE INVENTION
In order to clearly understand the evaluation of the synthesis of individual chemical structures; as well as the evaluation of the inhibition efficiency to corrosion of the corrosion inhibition formulation, object of the current invention, that is why, reference is made to the figure attached without limiting the scope of the invention:
Figure 1 illustrates the electrochemical cell used in the evaluation of corrosion inhibition evaluation.
DETAILED DESCRIPTION OF THE INVENTION
The current invention consists of synthetizing individual chemical structures and providing corrosion inhibitors compositions formulated from synthetized structures that belong to different chemical families: imidazoles, benzotriazoles and ionic liquids; the basic criteria for the design of said formulations is based on the knowledge of the effect that has a particular structure over the modification of involved phenomena in the corrosion process and synergy that is generated using together with one or more molecular structures belonging to a particular family, in this case the difference is mainly centered on the chain length or on structures belonging to one or more different families, situation where the inherent functionality to each compound family is taken advantage. The procedure for the obtention of each formulation comprises the following steps: a synthesis step of the structures used as an active
In order to clearly understand the evaluation of the synthesis of individual chemical structures; as well as the evaluation of the inhibition efficiency to corrosion of the corrosion inhibition formulation, object of the current invention, that is why, reference is made to the figure attached without limiting the scope of the invention:
Figure 1 illustrates the electrochemical cell used in the evaluation of corrosion inhibition evaluation.
DETAILED DESCRIPTION OF THE INVENTION
The current invention consists of synthetizing individual chemical structures and providing corrosion inhibitors compositions formulated from synthetized structures that belong to different chemical families: imidazoles, benzotriazoles and ionic liquids; the basic criteria for the design of said formulations is based on the knowledge of the effect that has a particular structure over the modification of involved phenomena in the corrosion process and synergy that is generated using together with one or more molecular structures belonging to a particular family, in this case the difference is mainly centered on the chain length or on structures belonging to one or more different families, situation where the inherent functionality to each compound family is taken advantage. The procedure for the obtention of each formulation comprises the following steps: a synthesis step of the structures used as an active
9 component; a step of incorporation of 1, 2 or 3 active components of the same or different chemical structure family; a step of incorporation of the solvent and a step of stirring up to the obtention of the complete integration of the formulation.
The composition object of the current invention are useful to control the internal corrosion in pipelines transporting crude oil wherein the content of associated water is from 0.2 to 40% and the concentration of inorganic salts (i.e. chlorides, sulfates, carbonates, among others) ranges from 10,000 and 70,000 ppm and wherein there is evidence of the presence of H2S and 02, as dissolved gases.
Two of the families of the compounds involved in the current invention belong to azoles and are mainly amine derivatives of imidazole and benzotriazole whereas the third belongs to ionic liquids; the structural characteristics of each family is described below:
lmidazole R
Po Wherein R is a saturated or unsaturated hydrophobic hydrocarbon chain containing 2 to 25 carbon atoms and can be lineal or branched.
R1 is hydrogen or a lineal or branched alkyl radical containing =
from 1 to 5 carbon atoms.
Benzotriazole N/
s \
IC ¨R
Wherein R is a saturated or unsaturated hydrophobic hydrocarbon chain containing 2 to 25 carbon atoms and can be lineal or branched, inclusively it can have internal substituents that
The composition object of the current invention are useful to control the internal corrosion in pipelines transporting crude oil wherein the content of associated water is from 0.2 to 40% and the concentration of inorganic salts (i.e. chlorides, sulfates, carbonates, among others) ranges from 10,000 and 70,000 ppm and wherein there is evidence of the presence of H2S and 02, as dissolved gases.
Two of the families of the compounds involved in the current invention belong to azoles and are mainly amine derivatives of imidazole and benzotriazole whereas the third belongs to ionic liquids; the structural characteristics of each family is described below:
lmidazole R
Po Wherein R is a saturated or unsaturated hydrophobic hydrocarbon chain containing 2 to 25 carbon atoms and can be lineal or branched.
R1 is hydrogen or a lineal or branched alkyl radical containing =
from 1 to 5 carbon atoms.
Benzotriazole N/
s \
IC ¨R
Wherein R is a saturated or unsaturated hydrophobic hydrocarbon chain containing 2 to 25 carbon atoms and can be lineal or branched, inclusively it can have internal substituents that
10 increase its corrosion inhibition properties of the original structure.
Examples of internal substituents are the amide and amine groups Ionic liquids X
.7' R ¨ Imidazole Wherein R is a saturated or unsaturated hydrophobic hydrocarbon chain containing 2 to 25 carbon atoms and can be lineal or branched.
R1 is hydrogen or a lineal or branched alkyl radical containing from 1 to 5 carbon atoms; X is a halogen, preferably Cl, Br or I.
This invention also considers the compositions where compounds from the imidazoles, benzotriazoles and ionic liquid
Examples of internal substituents are the amide and amine groups Ionic liquids X
.7' R ¨ Imidazole Wherein R is a saturated or unsaturated hydrophobic hydrocarbon chain containing 2 to 25 carbon atoms and can be lineal or branched.
R1 is hydrogen or a lineal or branched alkyl radical containing from 1 to 5 carbon atoms; X is a halogen, preferably Cl, Br or I.
This invention also considers the compositions where compounds from the imidazoles, benzotriazoles and ionic liquid
11 families are involved; these mixtures result in a binary or tertiary combination among members of the same or different families.
In the case of binary mixtures of the same families, the current invention refers to, but is not limited to, the following cases:
Formulations composed by the members of the imidazole amine derivatives family, family A, with general formula N
tl Wherein, for the first member of the composition, component Al, R is a saturated or unsaturated hydrophobic hydrocarbon chain containing from 2 to 10 carbon atoms but preferably from 4 to 8 carbon atoms; whereas for the second member of the composition, component A2, R is a saturated or unsaturated hydrophobic hydrocarbon chain containing from 11 to 25 carbon atoms, more preferably from 12 to 20 carbon atoms. In both cases, the hydrophobic hydrocarbon chain can be lineal or branched and R1 is, also for both members, a hydrogen or a lineal or branched alkyl radical containing from 1 to 5 carbon atoms.
The compositions are mixtures of components Al and A2 with a ratio that can be of 1:1, 1:2, 1:3, 3:1, 2:1.
Formulations composed by two members of amine derivatives of the benzotriazole family, family B, with general formula
In the case of binary mixtures of the same families, the current invention refers to, but is not limited to, the following cases:
Formulations composed by the members of the imidazole amine derivatives family, family A, with general formula N
tl Wherein, for the first member of the composition, component Al, R is a saturated or unsaturated hydrophobic hydrocarbon chain containing from 2 to 10 carbon atoms but preferably from 4 to 8 carbon atoms; whereas for the second member of the composition, component A2, R is a saturated or unsaturated hydrophobic hydrocarbon chain containing from 11 to 25 carbon atoms, more preferably from 12 to 20 carbon atoms. In both cases, the hydrophobic hydrocarbon chain can be lineal or branched and R1 is, also for both members, a hydrogen or a lineal or branched alkyl radical containing from 1 to 5 carbon atoms.
The compositions are mixtures of components Al and A2 with a ratio that can be of 1:1, 1:2, 1:3, 3:1, 2:1.
Formulations composed by two members of amine derivatives of the benzotriazole family, family B, with general formula
12 Wherein, for the first member of the composition, component 81, R is a saturated or unsaturated hydrophobic hydrocarbon chain containing from 2 to 10 carbon atoms, but preferably from 6 to 10 carbon atoms and it can be lineal or branched or inclusively can have internal substituents that increase the corrosion inhibition properties of the original structure; whereas, for the second member of the composition, component 82, R is a saturated or unsaturated hydrophobic hydrocarbon chain containing from 11 to 25, but preferably from 14 to 18 carbon atoms and can be lineal or branched and inclusively can have internal substituents that increase corrosion inhibition properties of the original structure. Examples of internal substituents are the amide and amine groups.
The compositions are mixtures of components B1 and B2 with a ratio that can be of 1:1, 1:2, 1:3, 3:1, 2:1.
Formulations composed by two members of amine derivatives from the ionic liquid family, family C, with general formula X
R ________________________________ Imidazote
The compositions are mixtures of components B1 and B2 with a ratio that can be of 1:1, 1:2, 1:3, 3:1, 2:1.
Formulations composed by two members of amine derivatives from the ionic liquid family, family C, with general formula X
R ________________________________ Imidazote
13 Wherein, for the first member of the composition, component Cl, R is a saturated or unsaturated hydrophobic hydrocarbon chain containing from 2 to 10, but preferably from 4 to 8 carbon atoms and can be lineal or branched; whereas for the second member of the composition, component C2, R is a saturated or unsaturated hydrophobic hydrocarbon chain containing from 11 to 25, but preferably from 14 to 18 carbon atoms and it can be lineal or branched.
For both components, R1 is hydrogen or a lineal or branched alkyl radical containing from 1 to 5 carbon atoms and X is halogen, preferably Cl, Br o I.
The compositions are mixtures of components B1 and B2 with a relation that can be of 1:1, 1:2, 1:3, 3:1 and 2:1.
In case of binary mixtures of different families, the current invention refers to, but is not limited to the following cases:
Formulations composed by members of amine derivatives from the imidazole and benzotriazole families.
The compositions are mixtures of the components Al and Bl;
Al and B2; A2 and B1 and A2 and B2, but preferably A2 and Bl, with the ratio from 1:3 to 3:1.
Formulations composed by members of amine derivatives from the imidazole and ionic liquid families.
The compositions are mixtures of the components Al and Cl;
Al and C2; A2 and Cl and A2 and C2, but preferably A2 and Cl, with the ratio from 1:3 to 3:1.
For both components, R1 is hydrogen or a lineal or branched alkyl radical containing from 1 to 5 carbon atoms and X is halogen, preferably Cl, Br o I.
The compositions are mixtures of components B1 and B2 with a relation that can be of 1:1, 1:2, 1:3, 3:1 and 2:1.
In case of binary mixtures of different families, the current invention refers to, but is not limited to the following cases:
Formulations composed by members of amine derivatives from the imidazole and benzotriazole families.
The compositions are mixtures of the components Al and Bl;
Al and B2; A2 and B1 and A2 and B2, but preferably A2 and Bl, with the ratio from 1:3 to 3:1.
Formulations composed by members of amine derivatives from the imidazole and ionic liquid families.
The compositions are mixtures of the components Al and Cl;
Al and C2; A2 and Cl and A2 and C2, but preferably A2 and Cl, with the ratio from 1:3 to 3:1.
14 Formulations composed by members of amine derivatives from the benzotriazoles and ionic liquid families.
The compositions are mixtures of the components B1 and Cl;
B1 and 02; B2 and Cl and B2 and C2, but preferably B2 and C2, with the ratio from 1:3 to 3:1.
In the case of ternary mixtures of molecules belonging to the same or different families, the current invention refers to, but is not limited to the following cases:
The compositions are mixtures of the following components Al, B1 and Cl; Al, B1 and C2; Al, B2 and Cl; Al, B2 and C2; A2, B1 and Cl; A2, B1 and 02; A2, B2 and Cl; A2, B2 and C2; Al, A2 and Bl; Al, A2 and B2; Al, A2 and Cl; Al, A2 and C2; Bl, B2 and Al;
Bl, B2 and A2; Bl, B2 and Cl; Bl, B2 and 02; Cl, C2 and Al; Cl, 02 and A2; Cl, C2 and Bl; and Cl ,C2 and B2, but preferably Al, A2 and Cl; Al, A2 and C2 and Bl, B2 and Cl and Bl, B2 and C2, with molar ratio from 1:1:1 to 2:1:1, 1:2:1, 1:1:2.
EXAMPLES
Below are described examples of the synthesis of basic structures belonging to the three families involved in corrosion inhibitor formulations and examples of binary and ternary formulations; as well as the evaluation of corrosion inhibition efficiency of the formulations and the individual components.
Example 1 Synthesis of imidazole amine derivatives Synthesis of N-VH-imidazole-(4-methylidene)J-hexane-1-amine 5 In a ball flask attached to a cooler with magnetic stirring, are placed 25 g of 4-imidazolcarboxaldehyde and 20 mL of methanol (Me0H) are added, are maintained in moderated stirring up to full dissolution; 32.5 mL of hexylamine are added, maintaining stirring and 15 additional mL of Me0H are added.
10 The reaction mixture is maintained under reflux for 9 hours at a temperature of 60 C, between the fourth and the sixth reflux hours; a Dean-Stark trap is placed to withdraw the H20 generated during the reaction.
Once concluded the reaction time, it is left at room temperature
The compositions are mixtures of the components B1 and Cl;
B1 and 02; B2 and Cl and B2 and C2, but preferably B2 and C2, with the ratio from 1:3 to 3:1.
In the case of ternary mixtures of molecules belonging to the same or different families, the current invention refers to, but is not limited to the following cases:
The compositions are mixtures of the following components Al, B1 and Cl; Al, B1 and C2; Al, B2 and Cl; Al, B2 and C2; A2, B1 and Cl; A2, B1 and 02; A2, B2 and Cl; A2, B2 and C2; Al, A2 and Bl; Al, A2 and B2; Al, A2 and Cl; Al, A2 and C2; Bl, B2 and Al;
Bl, B2 and A2; Bl, B2 and Cl; Bl, B2 and 02; Cl, C2 and Al; Cl, 02 and A2; Cl, C2 and Bl; and Cl ,C2 and B2, but preferably Al, A2 and Cl; Al, A2 and C2 and Bl, B2 and Cl and Bl, B2 and C2, with molar ratio from 1:1:1 to 2:1:1, 1:2:1, 1:1:2.
EXAMPLES
Below are described examples of the synthesis of basic structures belonging to the three families involved in corrosion inhibitor formulations and examples of binary and ternary formulations; as well as the evaluation of corrosion inhibition efficiency of the formulations and the individual components.
Example 1 Synthesis of imidazole amine derivatives Synthesis of N-VH-imidazole-(4-methylidene)J-hexane-1-amine 5 In a ball flask attached to a cooler with magnetic stirring, are placed 25 g of 4-imidazolcarboxaldehyde and 20 mL of methanol (Me0H) are added, are maintained in moderated stirring up to full dissolution; 32.5 mL of hexylamine are added, maintaining stirring and 15 additional mL of Me0H are added.
10 The reaction mixture is maintained under reflux for 9 hours at a temperature of 60 C, between the fourth and the sixth reflux hours; a Dean-Stark trap is placed to withdraw the H20 generated during the reaction.
Once concluded the reaction time, it is left at room temperature
15 and the solvent is evaporated at reduced pressure. The obtained product is yellow oil with a performance of 81%.
Example 2 Synthesis of N-VH-imidazole-(4-methylidene)J-decan-1-amine The same procedure described in example 1 is followed, using mL of decylamine instead of hexylamine.
The obtained performance in this case is of 78%.
Example 3 Synthesis of benzotriazole amine derivatives 25 Synthesis of N-(1H-benzotriazole-1-methyl)-octadecan-1-
Example 2 Synthesis of N-VH-imidazole-(4-methylidene)J-decan-1-amine The same procedure described in example 1 is followed, using mL of decylamine instead of hexylamine.
The obtained performance in this case is of 78%.
Example 3 Synthesis of benzotriazole amine derivatives 25 Synthesis of N-(1H-benzotriazole-1-methyl)-octadecan-1-
16 amine In a ball flask equipped with magnetic stirring, 17.5 g of 1H-Benzotriazole are placed maintaining a moderate stirring, 60 mL of methanol (Me0H) are added and stirring is continued for dissolution.
40 g of 1-octadecylamine are added, stirring is maintained up to the obtention of a slightly yellow crystalline solution and 20 mL of formaldehyde aqueous solution are added.
The mixture is maintained under stirring at room temperature during 2 hours; the reaction product precipitates as a soft solid, the solvent is removed by filtration and is dried at a temperature of 110 C during 2h. The performance is of 79%.
Example 4 Synthesis of N-(1H-benzotriazole-1-methyl)-hexane-1-amine The same procedure of the example 3 is followed, using 25 mL
de 1-hexylamine instead of 1-octadecylamine.
The product is viscous yellow oil with a performance of 89%.
Example 5 Synthesis of ionic liquids Synthesis of 1-alyI-3-methylimidazolium bromide In a 100 mL ball flask attached to a cooler and with magnetic stirring, 15 g of methylimidazolium dissolved of 25 mL of toluene are added; with the help of an addition funnel; 30 g of allyl bromide are incorporated, the reaction mixture is stirred and is taken at a temperature of 60 C, stirring is maintained for 1.0 hour.
The reaction mixture is washed twice with 10 mL of ethyl
40 g of 1-octadecylamine are added, stirring is maintained up to the obtention of a slightly yellow crystalline solution and 20 mL of formaldehyde aqueous solution are added.
The mixture is maintained under stirring at room temperature during 2 hours; the reaction product precipitates as a soft solid, the solvent is removed by filtration and is dried at a temperature of 110 C during 2h. The performance is of 79%.
Example 4 Synthesis of N-(1H-benzotriazole-1-methyl)-hexane-1-amine The same procedure of the example 3 is followed, using 25 mL
de 1-hexylamine instead of 1-octadecylamine.
The product is viscous yellow oil with a performance of 89%.
Example 5 Synthesis of ionic liquids Synthesis of 1-alyI-3-methylimidazolium bromide In a 100 mL ball flask attached to a cooler and with magnetic stirring, 15 g of methylimidazolium dissolved of 25 mL of toluene are added; with the help of an addition funnel; 30 g of allyl bromide are incorporated, the reaction mixture is stirred and is taken at a temperature of 60 C, stirring is maintained for 1.0 hour.
The reaction mixture is washed twice with 10 mL of ethyl
17 acetate and furthermore with 15 mL of ether. The solvent is removed with a Rotavapor .
The obtained product is dried at high vacuum, obtaining a yellow liquid with a performance of 92%.
Example 6 Synthesis of 1-decy1-3-methylimidazolium bromide The same procedure described in example 5 is used, but with the following reagents and quantities:
12 g of methylimidazolium 35 mL of toluene 22 g of bromodecane The reaction mixture is stirred and is taken to a temperature of 95 C and is maintained under stirring for 2 hours.
The following steps are similar to those of example 5. An amber liquid with a performance of 87.5% is obtained.
Example 7 Evaluation of corrosion inhibiting properties of individual structures and binary formulations object of the current invention Methodology of Evaluation Evaluation using electrochemical impedance spectroscopy (EIS) The evaluation of corrosion inhibiting properties of the individual structures and binary compositions was carried out in a conventional electrochemical cell (E) with a three electrode
The obtained product is dried at high vacuum, obtaining a yellow liquid with a performance of 92%.
Example 6 Synthesis of 1-decy1-3-methylimidazolium bromide The same procedure described in example 5 is used, but with the following reagents and quantities:
12 g of methylimidazolium 35 mL of toluene 22 g of bromodecane The reaction mixture is stirred and is taken to a temperature of 95 C and is maintained under stirring for 2 hours.
The following steps are similar to those of example 5. An amber liquid with a performance of 87.5% is obtained.
Example 7 Evaluation of corrosion inhibiting properties of individual structures and binary formulations object of the current invention Methodology of Evaluation Evaluation using electrochemical impedance spectroscopy (EIS) The evaluation of corrosion inhibiting properties of the individual structures and binary compositions was carried out in a conventional electrochemical cell (E) with a three electrode
18 arrangement as the one shown in Figure 1. This cell allows maintaining stirring and constant temperature during development of measurement.
The inhibiting formulations to be evaluated are added in the desired concentration in the test solution (D), whereas a stirring of 2000 rpm and a temperature of 40 C are maintained. Furthermore, it is submerged in a sample as a steel disk to the carbon previously destroyed with a 600 sandpaper, this sample has the function of a work electrode (B) in the electrochemical cell; the graphite auxiliary counter electrode (C) and the calomel saturated electrode (A) are placed as reference. The system is maintained under stirring and constant temperature for 3 hours.
After 3 hours, the electrochemical impedance spectrum is obtained in a range of 10 kHz and 10 mHz frequency and the resistance related to corrosion and together with that obtained in an identical experiment but only with the test solution was obtained from this spectrum; the corrosion inhibition efficiency was calculated.
Evaluation of behavior tests The binary and ternary compositions were evaluated through the following behavior tests, specific for this type of products:
Method of the wheel A sample of carbon steel to API 5L X52 with dimensions of 2.54 cm x 1.27 cm x 0.025 are weighed and a bottle with 180mL of test solution is placed, preferably a sample of the system where the
The inhibiting formulations to be evaluated are added in the desired concentration in the test solution (D), whereas a stirring of 2000 rpm and a temperature of 40 C are maintained. Furthermore, it is submerged in a sample as a steel disk to the carbon previously destroyed with a 600 sandpaper, this sample has the function of a work electrode (B) in the electrochemical cell; the graphite auxiliary counter electrode (C) and the calomel saturated electrode (A) are placed as reference. The system is maintained under stirring and constant temperature for 3 hours.
After 3 hours, the electrochemical impedance spectrum is obtained in a range of 10 kHz and 10 mHz frequency and the resistance related to corrosion and together with that obtained in an identical experiment but only with the test solution was obtained from this spectrum; the corrosion inhibition efficiency was calculated.
Evaluation of behavior tests The binary and ternary compositions were evaluated through the following behavior tests, specific for this type of products:
Method of the wheel A sample of carbon steel to API 5L X52 with dimensions of 2.54 cm x 1.27 cm x 0.025 are weighed and a bottle with 180mL of test solution is placed, preferably a sample of the system where the
19 inhibitor will be used, or an aggressive saline solution that simulates the acid, basic and neutral environments of the petroleum industry and a specific concentration of the corrosion inhibitor to be evaluated. The bottle is sealed and introduced in a temperature chamber with a 58.4 cm diameter wheel, provided with adequate and sufficient housing for 52 samples (bottles), the temperature of the chamber is increased at the desired value that preferably corresponds to the system operation temperature where the inhibitor is applied; the wheel rotation of 30 revolutions per minute was started during the heating process, that is maintained for a 24 hours period once the temperature is achieved.
At the end of the test, the sample is removed and washed consecutively with hexane, acetone, water, an inhibited solution of hydrochloric acid, a 5% potassium bicarbonate solution, is cleaned with water and soap using a plastic firm bristle swab, is rinsed with deionized water, is washed with acetone and is dried in an oven at 60 C for one hour, the sample is left to achieve room temperature and is weighed. With the difference of weight obtained in the sample in experiments without (blank) and with inhibitor, the corrosion inhibition efficiency was calculated.
Rotating cylinder, Rp / weight loss A cylindrical carbon steel speciemn API 5L X52 with dimensions of 0.793 cm in radius and 1 cm long, is introduced into the electrochemical cell, as the one shown in Figure 1 where previously the test solution was introduced, that would preferably correspond to a real sample of the system in which the inhibitor will be used and a known concentration of the inhibitor to evaluate. Rotation and temperature conditons are established depending on the system 5 conditions in which the inhibitor will be used and the corrosion inhibition efficiency is evaluated related to the blank experiment (absence of inhibitor) according to the standards ASTM D G 1, ASTM
D G 3, ASTM D G 5 y ASTM D G 59.
Similarly to the method of the wheel, the corrosion inhibition 10 efficiency can be evaluated by weight loss registering the initial weight of the cylindrical specimen and its weight after the before-mentioned cleaning procedure.
Table 1 shows the characterization of the waters used as test solutions in the evaluation that were carried out both with 15 independent structures and different formulations; whereas Table 2, shows some corrosion inhibitor results obtained with different concentrations of structures belonging to the three families, evaluated as the water identified as SP1 in Table 1.
Table 1, Characterization of real samples of water related to the crude transported in pipelines, these samples were used as test solutions in various evaluations of corrosion inhibition properties of the synthetized structures and formulations obtained thereof.
Analyte, Test solution mg/L SP1 SP2 SP3 Na 30,000 9,907 K 3,445 117 Specification Ca 1,980 118 ASTM-D 1141 "Substitute Ocean Mg 1,245 32 Water" + 600 mg/L
Mn 6.25 0 Sr 1,388 41 Analyte, Test solution mg/L SP1 SP2 SP3 Ba 52.1 0.53 Specification Fe 0.22 0.56 ASTM-D 1141 Cl 11,510 12,400 "Substitute Ocean SO4 2,930 1,310 Water" + 600 mg/L
NO3 2,810 0 H2S
pH 7.20 7.60 3.5 Corrosion NACE ID
182 72h 41.8 38.0 45.8 45 C, mpa Table 1. Corrosion inhibition efficiencies electrochemically evaluated with EIS using the test water SP1.
Concentration Inhibition Family Structure mg/L efficiency %
2500 95.4 IMC12 500 80.9 50 23.1 2500 98.0 Imidazole IMC14 500 78.9 50 19.8 2500 94.4 IMC18 500 84.5 50 20.2 2500 73.7 500 35.3 Benzotriaz 50 18.2 ole 2500 86.7 500 69.1 50 10.6 =
Concentration Inhibition Family Structure mg/L efficiency %
2500 96.2 500 97.4 50 55.8 BZC18 2500 98.6 inst 500 96.2 50 18.5 2500 76.0 MIMC4 500 61.9 50 15.2 2500 76.2 Ionic MIMC8 500 58.6 50 10.3 liquids 2500 89.3 MIMC12 500 77.7 50 12.4 2500 83.1 MIMC16 500 76.5 50 20.3 Example 8 Evaluation of corrosion inhibition properties of binary formulations Preparation of binary formulations In order to improve the corrosion inhibition efficiency that individually shows the structures at lower dosages, the following formulations between members of the same family and two different families were prepared:
Family IC12C14, wherein component Al is N-[1H-imidazole-(4-=
methylidenefl-dodecane-l-amine, whereas the component A2 is N-[1 H-imidazole-(4-methylidene)]-tetradecane-1-amine.
Ratio 1:0 Is prepared weighing 100 g of component Al and adding 67 mL of xylene, is moderately stirred to get full integration.
Ratio 3:1 Is prepared weighing 75 g of Al, 67 mL of xylene are added whereas it is moderately stirred, 25 g of component A2 are added and stirring is continued to get full integration.
Ratio 1:1 50 g of Al and 50 g of A2 are weighed, the preparation is similar to the last one.
Ratio 1:3 25 g of Al and 75 g of A2 are weighed, the preparation is similar to the last one.
Ration 0:1 100 g of A2 are weighed, the preparation is similar to the ratio 1:0.
Family BZC6C12, wherein component B1 is N-(1H-benzotriazole-l-methyl)-hexane-1-amine, whereas the component B2 is N-(1H-benzotriazole-1-methyl)-dodecane-1-amine.
The same ratio as those of family A are prepared, weighing in this case the same quantities but of the compounds B1 and B2 using methanol as solvent.
Family MIMC4C18, wherein component Cl is 1-buthy1-3-methylimidazolium bromide, whereas component C2 is 1-octadecy1-3-methylimidazolium bromide.
The same ratio as those of family A are prepared, weighing in this case the same quantities but of the compounds Cl and C2 using toluene as solvent.
Family BZC6MIMC4, wherein component Al is N-(1H-benzotriazole-1-methyl)-hexane-1-amine, whereas component Cl is 1-buthy1-3-methylimidazolium bromide.
The same ratio as those of family A are prepared, weighing in 5 this case the same quantities but of the compounds Al and Cl using 67 mL of a 50/50 mixture of methanol/toluene as solvent.
Family BZC12M1MC18, wherein component A2 is N-(1H-benzotriazole-l-methyl)-dodecane-1-amine, whereas component C2 is 1-octadecy1-3-methylimidazolium bromide.
10 The same ratio as those of family A are prepared, weighing in this case the same quantities but of the compounds A2 and C2 using 67 mL of a 50/50 mixture of methanol/toluene as solvent.
These formulations were evaluated with the same electrochemical methodology described in example 7 using SP1 test 15 solution and a dose of 50 mg/L of each one of them, the obtained corrosion inhibition results are shown in Table 3.
Table 3. Corrosion inhibition efficiencies of binary formulations, electrochemically evaluated with EIS technique using test water SP1 and a dose of 50 mg/L each.
20Inhibition efficiency, %
Family Formulation 1:0 3:1 1:1 1:3 0:1 Amine Imidazole IC12C14 95.5 87.0 93.2 92.3 98.0 Amine Benzotriazole BZC6C12 89.0 85.3 87.4 76.2 82.0 Ionic liquid MIMC4C18 76.0 50.9 70.9 92.0 83.0 Amine Benzotriazole/
BZC6MIMC4 89.0 91.1 90.8 92.2 76.0 Ionic liquid Amine Benzotriazole/ BZC12MIMC18 82.0 84.7 81.5 84.0 83.0 Ionic liquid Additionally, the formulations were evaluated by the method of the wheel (Wheel test) according to the NACE ID 182 specification using the test solution SP3 and a dosage of 50 ppm. Corrosion inhibition efficiencies obtained with this methodology are presented in Table 4.
Table 4, Corrosion inhibition efficiencies of binary formulations, evaluated with the method of the wheel (Wheel test) using test water SP3 and a dosage of 50 mg/L each. 72 hours of test at 45 C.
Inhibition efficiency, %
Family Formulation 1:0 3:1 1:1 1:3 0:1 Amine Imidazole IC12C14 71.6 85.4 83.4 87.7 81.9 Amine Benzotriazole BZC6C12 82.7 82.9 91.4 90.4 59.9 Methylimidazolium MIMC4C18 84.2 85.9 87.3 93.2 82.3 Amine Benzotriazole/
BZC6MIMC4 82.7 81.6 87.0 86.7 84.2 Methylimidazolium Amine Benzotriazole/
BZC12MIMC18 59.9 79.8 82.2 84.5 90.3 Methylimidazolium Example 9 Evaluation of corrosion inhibition properties of ternary formulations Preparation of ternary formulations Formulations of three components are prepared, wherein all components may belong to different families, or two of them belong to the same family whereas the other belong to another family.
Family 1C12BZC6MIMC4, wherein the component Al is N-[1H-imidazole-(4-methylidene)]-dodecane-l-amine; the component B1 is N-(1H-benzotriazole-l-methyl)-hexane-l-amine; and the component Cl is 1-buthy1-3-methylimidazolium bromide.
In order to prepare the 1:1:1 ratio, 33.3 g of Al are weighed and 22 mL of xylene are added; at moderate stirring, 33.3 g of B1 is added and stirring is continued adding 22 mL of methanol; finally, and maintaining stirring, 33.3 3 of Cl and 34 mL of toluene are added, stirring is continued up to complete integration.
Family 1C14BZC12MIMC18, wherein component A2 is N-[1H-imidazole-(4-methylidene)]-tetradecane-l-amine; the component B2 is N-(1H-benzotriazole-l-methyl)-dodecane-1-amine; and component C2 is 1-octadecy1-3-methylimidazolium bromide.
The procedure of the above formulation is followed but using components A2, B2 and C2.
Family BZC6C12MIMC4, wherein component B1 is N-(1H-benzotriazole-l-methyl)-hexane-1-amine; component B2 is N-(1H-benzotriazole-l-methyl)-dodecane-1-amine; and component Cl is 1-buthy1-3-methylimidazolium bromide.
The same procedure of the above formulation is followed but using components BI, B2 and Cl and methanol as solvent to solubilize compounds B and toluene.
Family BZC6C121C14, wherein component B1 is N-(1 H-benzotriazole-1-methyl)-hexane-1-amine; component B2 is N-(1H-benzotriazole-1-methyl)-dodecane-1-amine; A2 is N-[1H-imidazole-(4-methylidene)]-tetradecane-1-amine.
The procedure of the above formulation is followed but using components Bl, B2 and C2.
Family IC12C14BZC12, wherein component Al is N-[1 H-imidazole-(4-methylidene)]-dodecane-1-amine; component A2 is N-[1H-imidazole-(4-methylidene)]-tetradecane-l-amine; and component B2 is N-(1H-benzotriazole-l-methyl)-dodecane-1-amine.
The procedure of the above formulation is followed but using components Al, A2 and B2 and xylene to solubilize compounds A and methanol as solvents.
Family 1C12C14MIMC18, wherein component Al is N-[1H-imidazole-(4-methylidene)]-dodecane-l-amine; component A2 is N-[1H-imidazole-(4-methylidene)]-tetradecane-l-amine; and component C2 is 1-octadecy1-3-methylimidazolium bromide.
The procedure of the above formulation is followed but using components Al, A2 and C2 and xylene to solubilize compounds A and toluene as solvents.
The evaluation of the corrosion inhibition efficiency, using a dosage of 50 mg/L of these formulations in various behavioral tests and with different media is shown in Table 5.
Table 5, Corrosion inhibition efficiencies of ternary formulations evaluated with test methods: rotating cylinder, wheel (Wheel test) and Electrochemical (EIS) using test solutions SP1, SP2 and SP3, as indicated, and a dosage of 50 mg/L of each formulation.
% of corrosion inhibition efficiency Rotating cylinder Method of the ASTM G 185 wheel NACE
ID EIS
Formulation Medium: SP1 182 Medium:
Weight Rp SP1 SP2 SP3 loss 1C12BZC6MIMC4 90.8 96.3 95.9 96.6 93.6 99.9 93.5 94.7 97.3 95.2 96.1 98.9 BZC6C12MIMC4 96.7 90.5 93.2 90.9 91.7 97.2 BZC6C121C14 91.1 96.1 92.9 94.3 95.0 99.0 IC12C14BZC12 95.8 96.5 91.4 92.6 93.3 98.3 1C12C14M1MC18 93.1 92.0 90.4 95.4 94.5 99.7
At the end of the test, the sample is removed and washed consecutively with hexane, acetone, water, an inhibited solution of hydrochloric acid, a 5% potassium bicarbonate solution, is cleaned with water and soap using a plastic firm bristle swab, is rinsed with deionized water, is washed with acetone and is dried in an oven at 60 C for one hour, the sample is left to achieve room temperature and is weighed. With the difference of weight obtained in the sample in experiments without (blank) and with inhibitor, the corrosion inhibition efficiency was calculated.
Rotating cylinder, Rp / weight loss A cylindrical carbon steel speciemn API 5L X52 with dimensions of 0.793 cm in radius and 1 cm long, is introduced into the electrochemical cell, as the one shown in Figure 1 where previously the test solution was introduced, that would preferably correspond to a real sample of the system in which the inhibitor will be used and a known concentration of the inhibitor to evaluate. Rotation and temperature conditons are established depending on the system 5 conditions in which the inhibitor will be used and the corrosion inhibition efficiency is evaluated related to the blank experiment (absence of inhibitor) according to the standards ASTM D G 1, ASTM
D G 3, ASTM D G 5 y ASTM D G 59.
Similarly to the method of the wheel, the corrosion inhibition 10 efficiency can be evaluated by weight loss registering the initial weight of the cylindrical specimen and its weight after the before-mentioned cleaning procedure.
Table 1 shows the characterization of the waters used as test solutions in the evaluation that were carried out both with 15 independent structures and different formulations; whereas Table 2, shows some corrosion inhibitor results obtained with different concentrations of structures belonging to the three families, evaluated as the water identified as SP1 in Table 1.
Table 1, Characterization of real samples of water related to the crude transported in pipelines, these samples were used as test solutions in various evaluations of corrosion inhibition properties of the synthetized structures and formulations obtained thereof.
Analyte, Test solution mg/L SP1 SP2 SP3 Na 30,000 9,907 K 3,445 117 Specification Ca 1,980 118 ASTM-D 1141 "Substitute Ocean Mg 1,245 32 Water" + 600 mg/L
Mn 6.25 0 Sr 1,388 41 Analyte, Test solution mg/L SP1 SP2 SP3 Ba 52.1 0.53 Specification Fe 0.22 0.56 ASTM-D 1141 Cl 11,510 12,400 "Substitute Ocean SO4 2,930 1,310 Water" + 600 mg/L
NO3 2,810 0 H2S
pH 7.20 7.60 3.5 Corrosion NACE ID
182 72h 41.8 38.0 45.8 45 C, mpa Table 1. Corrosion inhibition efficiencies electrochemically evaluated with EIS using the test water SP1.
Concentration Inhibition Family Structure mg/L efficiency %
2500 95.4 IMC12 500 80.9 50 23.1 2500 98.0 Imidazole IMC14 500 78.9 50 19.8 2500 94.4 IMC18 500 84.5 50 20.2 2500 73.7 500 35.3 Benzotriaz 50 18.2 ole 2500 86.7 500 69.1 50 10.6 =
Concentration Inhibition Family Structure mg/L efficiency %
2500 96.2 500 97.4 50 55.8 BZC18 2500 98.6 inst 500 96.2 50 18.5 2500 76.0 MIMC4 500 61.9 50 15.2 2500 76.2 Ionic MIMC8 500 58.6 50 10.3 liquids 2500 89.3 MIMC12 500 77.7 50 12.4 2500 83.1 MIMC16 500 76.5 50 20.3 Example 8 Evaluation of corrosion inhibition properties of binary formulations Preparation of binary formulations In order to improve the corrosion inhibition efficiency that individually shows the structures at lower dosages, the following formulations between members of the same family and two different families were prepared:
Family IC12C14, wherein component Al is N-[1H-imidazole-(4-=
methylidenefl-dodecane-l-amine, whereas the component A2 is N-[1 H-imidazole-(4-methylidene)]-tetradecane-1-amine.
Ratio 1:0 Is prepared weighing 100 g of component Al and adding 67 mL of xylene, is moderately stirred to get full integration.
Ratio 3:1 Is prepared weighing 75 g of Al, 67 mL of xylene are added whereas it is moderately stirred, 25 g of component A2 are added and stirring is continued to get full integration.
Ratio 1:1 50 g of Al and 50 g of A2 are weighed, the preparation is similar to the last one.
Ratio 1:3 25 g of Al and 75 g of A2 are weighed, the preparation is similar to the last one.
Ration 0:1 100 g of A2 are weighed, the preparation is similar to the ratio 1:0.
Family BZC6C12, wherein component B1 is N-(1H-benzotriazole-l-methyl)-hexane-1-amine, whereas the component B2 is N-(1H-benzotriazole-1-methyl)-dodecane-1-amine.
The same ratio as those of family A are prepared, weighing in this case the same quantities but of the compounds B1 and B2 using methanol as solvent.
Family MIMC4C18, wherein component Cl is 1-buthy1-3-methylimidazolium bromide, whereas component C2 is 1-octadecy1-3-methylimidazolium bromide.
The same ratio as those of family A are prepared, weighing in this case the same quantities but of the compounds Cl and C2 using toluene as solvent.
Family BZC6MIMC4, wherein component Al is N-(1H-benzotriazole-1-methyl)-hexane-1-amine, whereas component Cl is 1-buthy1-3-methylimidazolium bromide.
The same ratio as those of family A are prepared, weighing in 5 this case the same quantities but of the compounds Al and Cl using 67 mL of a 50/50 mixture of methanol/toluene as solvent.
Family BZC12M1MC18, wherein component A2 is N-(1H-benzotriazole-l-methyl)-dodecane-1-amine, whereas component C2 is 1-octadecy1-3-methylimidazolium bromide.
10 The same ratio as those of family A are prepared, weighing in this case the same quantities but of the compounds A2 and C2 using 67 mL of a 50/50 mixture of methanol/toluene as solvent.
These formulations were evaluated with the same electrochemical methodology described in example 7 using SP1 test 15 solution and a dose of 50 mg/L of each one of them, the obtained corrosion inhibition results are shown in Table 3.
Table 3. Corrosion inhibition efficiencies of binary formulations, electrochemically evaluated with EIS technique using test water SP1 and a dose of 50 mg/L each.
20Inhibition efficiency, %
Family Formulation 1:0 3:1 1:1 1:3 0:1 Amine Imidazole IC12C14 95.5 87.0 93.2 92.3 98.0 Amine Benzotriazole BZC6C12 89.0 85.3 87.4 76.2 82.0 Ionic liquid MIMC4C18 76.0 50.9 70.9 92.0 83.0 Amine Benzotriazole/
BZC6MIMC4 89.0 91.1 90.8 92.2 76.0 Ionic liquid Amine Benzotriazole/ BZC12MIMC18 82.0 84.7 81.5 84.0 83.0 Ionic liquid Additionally, the formulations were evaluated by the method of the wheel (Wheel test) according to the NACE ID 182 specification using the test solution SP3 and a dosage of 50 ppm. Corrosion inhibition efficiencies obtained with this methodology are presented in Table 4.
Table 4, Corrosion inhibition efficiencies of binary formulations, evaluated with the method of the wheel (Wheel test) using test water SP3 and a dosage of 50 mg/L each. 72 hours of test at 45 C.
Inhibition efficiency, %
Family Formulation 1:0 3:1 1:1 1:3 0:1 Amine Imidazole IC12C14 71.6 85.4 83.4 87.7 81.9 Amine Benzotriazole BZC6C12 82.7 82.9 91.4 90.4 59.9 Methylimidazolium MIMC4C18 84.2 85.9 87.3 93.2 82.3 Amine Benzotriazole/
BZC6MIMC4 82.7 81.6 87.0 86.7 84.2 Methylimidazolium Amine Benzotriazole/
BZC12MIMC18 59.9 79.8 82.2 84.5 90.3 Methylimidazolium Example 9 Evaluation of corrosion inhibition properties of ternary formulations Preparation of ternary formulations Formulations of three components are prepared, wherein all components may belong to different families, or two of them belong to the same family whereas the other belong to another family.
Family 1C12BZC6MIMC4, wherein the component Al is N-[1H-imidazole-(4-methylidene)]-dodecane-l-amine; the component B1 is N-(1H-benzotriazole-l-methyl)-hexane-l-amine; and the component Cl is 1-buthy1-3-methylimidazolium bromide.
In order to prepare the 1:1:1 ratio, 33.3 g of Al are weighed and 22 mL of xylene are added; at moderate stirring, 33.3 g of B1 is added and stirring is continued adding 22 mL of methanol; finally, and maintaining stirring, 33.3 3 of Cl and 34 mL of toluene are added, stirring is continued up to complete integration.
Family 1C14BZC12MIMC18, wherein component A2 is N-[1H-imidazole-(4-methylidene)]-tetradecane-l-amine; the component B2 is N-(1H-benzotriazole-l-methyl)-dodecane-1-amine; and component C2 is 1-octadecy1-3-methylimidazolium bromide.
The procedure of the above formulation is followed but using components A2, B2 and C2.
Family BZC6C12MIMC4, wherein component B1 is N-(1H-benzotriazole-l-methyl)-hexane-1-amine; component B2 is N-(1H-benzotriazole-l-methyl)-dodecane-1-amine; and component Cl is 1-buthy1-3-methylimidazolium bromide.
The same procedure of the above formulation is followed but using components BI, B2 and Cl and methanol as solvent to solubilize compounds B and toluene.
Family BZC6C121C14, wherein component B1 is N-(1 H-benzotriazole-1-methyl)-hexane-1-amine; component B2 is N-(1H-benzotriazole-1-methyl)-dodecane-1-amine; A2 is N-[1H-imidazole-(4-methylidene)]-tetradecane-1-amine.
The procedure of the above formulation is followed but using components Bl, B2 and C2.
Family IC12C14BZC12, wherein component Al is N-[1 H-imidazole-(4-methylidene)]-dodecane-1-amine; component A2 is N-[1H-imidazole-(4-methylidene)]-tetradecane-l-amine; and component B2 is N-(1H-benzotriazole-l-methyl)-dodecane-1-amine.
The procedure of the above formulation is followed but using components Al, A2 and B2 and xylene to solubilize compounds A and methanol as solvents.
Family 1C12C14MIMC18, wherein component Al is N-[1H-imidazole-(4-methylidene)]-dodecane-l-amine; component A2 is N-[1H-imidazole-(4-methylidene)]-tetradecane-l-amine; and component C2 is 1-octadecy1-3-methylimidazolium bromide.
The procedure of the above formulation is followed but using components Al, A2 and C2 and xylene to solubilize compounds A and toluene as solvents.
The evaluation of the corrosion inhibition efficiency, using a dosage of 50 mg/L of these formulations in various behavioral tests and with different media is shown in Table 5.
Table 5, Corrosion inhibition efficiencies of ternary formulations evaluated with test methods: rotating cylinder, wheel (Wheel test) and Electrochemical (EIS) using test solutions SP1, SP2 and SP3, as indicated, and a dosage of 50 mg/L of each formulation.
% of corrosion inhibition efficiency Rotating cylinder Method of the ASTM G 185 wheel NACE
ID EIS
Formulation Medium: SP1 182 Medium:
Weight Rp SP1 SP2 SP3 loss 1C12BZC6MIMC4 90.8 96.3 95.9 96.6 93.6 99.9 93.5 94.7 97.3 95.2 96.1 98.9 BZC6C12MIMC4 96.7 90.5 93.2 90.9 91.7 97.2 BZC6C121C14 91.1 96.1 92.9 94.3 95.0 99.0 IC12C14BZC12 95.8 96.5 91.4 92.6 93.3 98.3 1C12C14M1MC18 93.1 92.0 90.4 95.4 94.5 99.7
Claims (15)
1. A corrosion inhibition composition for pipelines, process of elaboration and synthesis; characterized in that the procedure for obtaining each formulation comprises the following stages: a stage of synthesis of structures used as an active component; a step of addition of 1, 2 or 3 active components of the same family or of different chemical structure family; a step of incorporating a solvent and a stirring stage until full integration of the formulation is achieved.
2. A corrosion inhibition composition for pipelines, process of elaboration and synthesis according to claim 1 characterized in that the inhibitors are basically constituted by compounds of molecular structure families, such as: imidazoles, benzotriazoles and ionic liquids; the formulations can include 2 or more components of each family and use as alcohol solvents, xylene, toluene of combinations thereof.
3. A corrosion inhibition composition for pipelines, process of elaboration and synthesis according to claims 1 a 2, characterized in that it controls the corrosion of metallic surfaces of the pipelines containing congenital water concentrations from 0.2 to 40% by weight; the salt concentrations of 10,000 to 70,000 ppm and hydrogen sulfate concentrations from 0 and 600 ppm.
4. A corrosion inhibition composition for pipelines, process of elaboration and synthesis according to claims 1 a 3, characterized in that 2 of the families of the involved compounds belong to azoles and are mainly amine derivatives of imidazole and benzotriazole.
5. A corrosion inhibition composition for pipelines, process of elaboration and synthesis according to claims 1 to 4, characterized in that the third family belongs to ionic liquids.
6. A corrosion inhibition composition for pipelines, process of elaboration and synthesis according to claims 1 to 5, characterized in that comprises a family of basic compounds with corrosion inhibition properties, amine derivatives of imidazole with the structure:
wherein R is a saturated or unsaturated hydrophobic hydrocarbon chain containing 2 to 25 carbon atoms and can be lineal or branched; and R1 is hydrogen or a lineal or branched alkyl radical containing from 1 to 5 carbon atoms.
wherein R is a saturated or unsaturated hydrophobic hydrocarbon chain containing 2 to 25 carbon atoms and can be lineal or branched; and R1 is hydrogen or a lineal or branched alkyl radical containing from 1 to 5 carbon atoms.
7. A corrosion inhibition composition for pipelines, process of elaboration and synthesis according to claims 1 a 6, characterized in that comprises a family of basic compounds with amine derivative corrosion inhibition properties of benzotriazole with the structure wherein R is a saturated or unsaturated hydrophobic hydrocarbon chain containing 2 to 25 carbon atoms and can be lineal or branched, inclusively it can have internal substituents that increase its corrosion inhibition properties of the original structure.
8. A corrosion inhibition composition for pipelines, process of elaboration and synthesis according to claims 1 to 7, characterized in that the internal substituents are amide and amine groups.
9. A corrosion inhibition composition for pipelines, process of elaboration and synthesis according to claims 1 a 8, characterized in that comprises a family of basic compounds with corrosion inhibition properties derived from ionic liquids with the structure wherein R is a saturated or unsaturated hydrophobic hydrocarbon chain containing 2 to 25 carbon atoms and can be lineal or branched; and R1 is hydrogen or a lineal or branched alkyl radical containing from 1 to 5 carbon atoms and X is a halogen, preferably CI, Br or I.
10. A group of basic compounds, according to claims 1 to 9 that have corrosion inhibition properties in typical environment of crude oil transportation.
11. The use of basic compounds according to claims 1 to 10 as substances able to inhibit corrosion, at moderate doses (500 to 2500 mg/L), in typical environment of crude oil transportation.
12. The use of a series of binary formulations according to claims 1 to 11 that take advantage of the synergies between members of two families to integrate corrosion inhibitors for typical environments of crude oil transportation.
13. The use of a series of binary formulations according to claims 1 to 12, able to inhibit corrosion typical environments of crude oil transportation at 80% with low doses (50 mg/L).
14. The use of a series of ternary formulations according to claims 1 to 13 that take advantage of the synergies between members of three families to integrate corrosion inhibitors for typical environments of crude oil transportation.
15. The use of a series of formulations according to claims 1 to 14, able to inhibit corrosion in typical environments of crude oil transportation at least in 90% at low doses (50 mg/L).
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