CA2060580C - Ammonium salt of an alkenylsuccinic half-amide and the use thereof as corrosion inhibitor in oil and/or gas production technology - Google Patents
Ammonium salt of an alkenylsuccinic half-amide and the use thereof as corrosion inhibitor in oil and/or gas production technology Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
- C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
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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
- C23F11/145—Amides; N-substituted amides
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Abstract
An ammonium salt of an alkenylsuccinic half-amide of formula (I) below
Description
I~~~~ AKTIENfiESELLSChIAFT O.Z. ooso/42171 ~rnr~toniur~ Spit of an Aikeny6suc~inic i°9~If-~nnid~
end the lJse Thereof as corrosion inhibitor in ail and/or has production ~e~hnol~gy The inventian relates to ammonium salts of alkenyl :>uccinic half-amides and to the use thereof as corrosion inhibitors in oil andlor gas production tech-nology to combat corrosion by media containing CCf2 and HZS and possibly elemental sulfur.
In the production of petroleum and natural gas there usually occurs an oil/water or gas/water mixture which in the case of oil may contain up to about 98% of water.
,° The salinity of the entrained water may be extremely low or conversely, the water may comprise a saturated salt solution. HZS and/or C02 are also present.
The combination of HZS and/or COZ and the water has a strong corrosive ,5 action on metals used in petroleum and natural gas plants. This action is intensified by the presence of elemental sulfur.
It is common practice to inject a solution or dispersion of corrosion inhibitor into the corrosive medium to be handled in the production, transport aad z° storage of petroleum or natural gas. By this means the surface of the metals contacted by the medium is coated with a protective film.
Hitherto, certain imidazoline salts have been proposed for this purpose (cf.
EP 0,065,191 and EP 0,103,737), but these have an unsatisfactory z5 anticorrosive effect against C02 and/or hlzS, especially in the presence of elemental sulfur, as discussed in Environment Treatment ~ Control, Feb.
1990, pp. 43 to 52.
Neither do amine salts of maleamide acids, as described in ~P 0,106,234, 3° possess adequate anticorrosive properties for this purpose.
Oil-soluble amidoamine salts of alkenylsuccinic acids and the use thereof as corrosion inhibitors in water-in-oil emulsions such as occur in oil production are described in EP 0, 359, 043.
~IVater-soluble alkanolamine salts of alkenyisuccinic acids, described in DE
~~~~ AKTIEN~ESELLSCHAFT 2 O.Z, ooso/42171 2,943,963-C2 as being effective as corrosion inhibitors in metal working, also show inadequate anticorrosive action in the systems under consideration here.
It is thus an object of the invention to provide improved, preferably water-soluble inhibitors for use in corrosive media such as occur in petroleum and/or natural gas production, to counteract the corrosive action of CrJ~
and/or H2S, especially when elemental sulfur is present.
,o We have now found that ammonium salts of alkenylsuccinic half-amides of formula (I) below o R~ C-O~A~-H
NCH/ (I) ,s /CH ~
R~ C=0 I
X
in which ZU
R~ denotes H or a Ce-C~~-aikenyl radial, provided that the radicals R' are not both H or both Cg-C~e-alkenyl, X denotes 'a group of the formula -i~HR2 or -fVR2R3, in which R2 and R3 denote C~-CB-alkyl, cycloalkyi or a heterocyclic ring attached to the nitrogen atom via an alkylene chain, and A denotes XH or a different amine of the formula Rn-~ /
ERs in which R4, R5 and Rg independently denote H, C~-Cs-alkyl (in which case R5 and R6 may together form a heterocyclic ring enclosing the nitrogen atom), C~-Cao-hydroxyaikyl or b --~(CH2)~-~N--~(CH2)~-~1H2 , R~
in which R~ denotes H or C~-C3-alkyl, n is an integer from 2 to 4, and m is an integer from 1 to 5, are particularly well suited for use as water-soluble corrosion inhibitors in oil and/or gas production plants.
A particularly suitable representative of the group X is a group of the formula (1l> below H
--N\ / (CH2)r \
(CH2)Q--N~ ~Y (1l), (CH2)p in which q is an integer from 1 to 4, r and p are independently 1 or 2, and Y denotes CRa2, NR$ (where R$ is H or C~-C3-alkyl), O or S.
The present invention also concerns a method of inhibiting corrosion in metals which are in contact with corrosive 20 oil/water or gas/water mixtures found in the production, transport and storage of petroleum and natural gas which comprises: injecting into the corrosive mixture a corrosion inhibiting amount of an ammonium salt of an alkenyl succinic half amide of the formula (I) as defined below, R ~ /C-O~A~-H
i H (I) /CH ~
R~ C=0 X
a in which:
Rl denote; H or_ a C6--c~'1g-alkenyl radical, provided that the radicals R~- :ire not both H or both C6-Cl0-alkenyl, X denotes a grc.-~.y> of t:he formula ( I I ) H
-i~J~ (CH2)r v (CH2)q ~~~, j Y ( I I ), (CH2)p in which q is a.n integer from 1 to 4, r and p are independently J cr ?, and Y denotes CR8~, NR8 (where R8 is F~ or C~_-C j--alkyl) , O or S, and A denotes XH or a d.i.ff_erent amine of t-me formula:
R4-N ,, ,,~Rs in which:
R4, R-'' and R6 independe~zt'_y denote H C1-C6-alkyl (in which case R5 <:~n.d RE~ may toger_iner form a heterocyclic ring including the nit:rc~g~n atone to which they are connected) , Cl--':1,,~-iaydro~:ya:lk:~,r:l- or ..-~-ICH2)n~(CH2)n.-NH2 in which R~ der~ot--cps H c>r ~l--C'_s--a~~.kyl, n is an integer from .L to 4, and m is an inl~ege.r ,=rom 1 to I.
It is part:~cularly adlrantagec~Lr~~ whc_n the group X or the above formLa=La ( T ) i- a rad:icai c>f fo:rrnula ( I I I ) below 3b H
CH2--~H2--~l\ ~N H ( I I I ).
The counterion A°-H is derived either from the amine XH used to form the half-amide or from a different amine of the formula R4-N.
.v Rs ~U
in which R4, R' and Rs have the meanings stated above. Such amines are NH3 or primary, secondary, ar tertiary amines, eg butylamine or dibutylamine, or alkanolamines, eg ethanolamine, diethanolamine, or triethanolamine, or they are polyamines such as diethylenetriamine or dipropylenetriamine.
The alkenylsuccinic amides forming the basis of the salts of the invention are obtained by the following method:
,.' ,r ~~SF AKTIENLiESELLSCHAFT n O.Z, ooso/n2171 1. The endothermic reaction, known per se, between malefic anhydride and the appropriate olefin is carried out at a temperature of from 150° to 250°C under standard pressure conditions or at a temperature of from 150° to 300°C in an autoclave das described in, say, DE A 3, 411, 53 ~ ) and 2. the alkenylsuccinic anhydride thus obtained is reacted with the amine XH
to form the aikenylsuccinic half-amide at a temperature of from 50° to 150°C, preferably from 50° to 120°C, for example in substance or in an ,o aromatic solvent.
The amide/ammonium salts of the invention are obtained therefrom by reaction with the amines A, preferably also at a temperature of from 50° to 120°C. When the same amine components are used for XH and A, the ,3 preparation of the amide/ammonium salt may be effected directly by reacting the alkenylsuccinic anhydride with the amine in a ratio of 1:2.
Particularly noteworthy examples of amines XH are aminoalkylpiperazines and aminoalkylmorpholines, for example aminoethylpiperazine.
2a The inhibitors thus obtained exhibit excellent anticorrosive action against HZS
and COa, and in particular, no impairment of this action is caused by the presence of elemental sulfur.
25 The efificacy of the inhibitors, particularly in the presence of elemental sulfur, can be increased by formulating the products with surface-active substances.
Suitable dispersing agents are: low molecular-weight or polymeric anionic 3o surfactants and dispersing agents, particularly alkylsuffonic acids, alkylarylsul fonic acids, arylsulfonic acids, and the salts thereof.
The corrosion inhibitors of the invention are used in amounts varying from 3 to 1000 ppm depending on the composition of the corrosive modium. To 3s combat corrosion by COx or C02/H2S only, the addition of inhibitor formula-tion is preferably from 5 to 50 ppm, and in the presence of elemental sulfur it is preferably from 100 to 300 ppm.
The invention is illustrated by the following Examples.
;p~ 20~~~~Q
~~~F AKTIENOESELLSCHAFT 5 O.Z.0050/42171 1. Ammonium salt synthesis Example 1 2.3 g of phenothiazine were added to a reaction mixture o~f eguimolar amounts of tetrameric propylene (463 g) and malefic anhydride (269.5 g), and the whole was stirred at a temperature of from 180° to 200°C
over a period of from 25 to 30 hours. Unconverted educts were then distilled off at 175°C under a high vacuum.
,0 A mixture of 342 g of the resulting alkenylsuccinic anhydride and 400 mi of xylene was heated to 80°C, and 368 g of aminoethylpiperazine were added dropwise at this temperature. Stirring was continued 'for 3 hours at the same temperature, and a portion of the solvent was removed under a water jet ,5 vacuum. There was obtained a black viscous product in a yield of 608 g and having a content of 85% of active ingredient.
The tetrameric propylene used was the C12 cut from the olefin oligomer-ization.
z0 as Composition (GC/MS analysis): C9 0.5%; Clo 5.8%; C11 20.7%; C12 70.9%;
C13 2.1 %.
The composition and isomer ratio may vary slightly from batch to batch.
The IR spectrum clearly indicates that the reaction product obtained from the alkenylsuccinic anhydride and aminoethylpiperazine is an ammonium salt of the alkenylsuccinic half-amide, since it shows both characteristic amide bands and -C02 bands. Imide formation is also indicated.
Characteristic IR bands:
Amide: 1680 to 1630 and '1570 to 1515 cm~l C00-: 1610 to 1550 cm°1 Imide: approx. 1770 to approx. 1700 cm-' .
The ammonium salts of the invention can be isolated from the reaction solution by conventional means.
Exarr~pBe 2 387 g of trimeric butylene (prepared by trimerization of n-butane) and 225 g b II~~~~AKTIENQESELLSCHAFT ' 6 ~',~ O.Z.005p/~2~~~
of malefic anhydride were placed in an autoclave. A nitrogen pressure of 5 bar was established, and the reaction mixture was stirred for 10 hours at a temperature of 200°C.
595 g of the reaction product were dissolved in 300 ml of xylene, and the solution was heated to 80°C. 578 g of aminoethyipiperazine were added dropwise at this temperature. The reaction mixture was stirred for 4 hours at the same temperature, after which a portion of the solvent was removed under a water jet vacuum to give the desired corrosion inhibitor as a dark ,° colored viscous oil.
Example 3 Example 2 was repeated except that a linear C»-olefin was used in place ,5 of trimeric butylene.
Exxaraiple ~
An alkenyisuccinic anhydride was prepared frorr~ trimeric butylene and Zp malefic anhydride as described in Example 2. Unconverted olefin and anhydride were removed at 100°C/30 mbar.
198 g (0.75 mole) of this product were dissolved in xylene, and the solution was heated to 100°C. 97 g (0.75 mole) of aminoethylpiperazine were slowly 25 added dropwise at this temperature. The reaction solution was then stirred for about 5 hours at 90-100°C. The solvent was then removed to give 290 g of a black viscous reaction product.
3o In order to neutralize the free carboxyl groups, 101 g (0.2 mole) of this product wore reacted with 26 g (0.2 mote) of diethylenetriamine in xylene at 80°C. The product was concentrated in a rotary evaporator to about 83%
to give the corrosion inhibitor of the invention in the form of a black viscous oil.
2. Examples of application The inhibitor formulations were tested dynamically using the "wheel-test"
described, for example, in EP A 0,359,048, which is a common method of 4° testing corrosion inhibitors in petroleum and natural gas production plants.
The test coupons were large steel plates of ST 37 which had previously been thoroughly ground with emery, degreased with toluene, and weighed.
I~~~FAKTIENQESELLSCHAFT 7 0.2.0050/42171 The coupons were then placed in the corrosive medium and were agitated therein for 16 hours at 80°C (40 rpm via a shaft coupled to rotate the test vessel). The specimens were then cleaned with an inhibited acid, degreased, dried, and weighed in order to determine the weight loss. The results were compared with reference values obtained in a test carried out without the addition of inhibitor.
,°
The anticorrosive factor Z in percent was calculated from the weighings using the following equation:
z = ~° G G~ x 100 [~o~
where G° is the rate of corrosion without inhibitor and G~ is the rate of corrosion with inhibitor.
The results are listed in the Tables below.
TABLE 1 - Anticorrosive factor Z [%J
Medium:
z 10% white 90% brine (3! NaCI?; and/or H25 spirit, saturated with C02 Saturated with:C02/CO2 CO2/H2S
Inhibitor dosage:3 ppm 7.5 ppm 3 ppm 7.5 ppm Product from Example 1 46 78 68 79 Example 2 51 75 74 80 F.~cample 3 61 64 76 81 Example 4 80 80 b ~~~FAKTIENQESELLSCHAFT 8 - O.Z.0050/421%1 TABI_~ 2 Medium: approx. 6.5 ml of brine saturated with H2S, approx. 193,5 ml of brine saturated with C02 , 0.5 g of ground sulfur Inhibitor dosage:150 ppm Product from Dispersing agent Anticorrosive factor Z L%J
Example 1 - 50 Example 1 10! oiigomeric aryl sulfonate 82 (Tamol 941 Oa) Example 1 15% alkylbenzene sulfonate 78 (ALBS) ,0 Example 2 10% oligomeric aryl sulfonate 85 Example ~ 15% ALBS 78 Example 3 15% ALBS 80 Example 3 10% oligomeric aryl sulfonate 75 Examale 4 15% ALBS 80 ,5 Comparative Examples Medium: approx. 6.5 ml of brine saturated with H2S, approx. 193.5 ml of brine saturated with C02, 0.5 g of ground sulfur Z° Inhibitor dosage: 150 ppm Product Dispersing agent Anticorrosive factor [%7 1. acetate of a long-chain - 17 imidazoline 2. amido-imidazoline plus - 33 Z5 dimerized/trimerized fatty acid 3. amido-imidazoline - 25 4. as for 1 10% oligomeric aryl 0 sulfonate 3° 5. as for 1 15% alkylbenzene 12 sulfonate It can be seen from the above results that the commercially available corrosion inhibitors are distinctly less effective and that the addition of 35 dispersing agents to said prior art corrosion inhibitors has no advantageous effect.
By comparison, the ammonium salts of the invention are found to be highly effective corrosion inhibitors.
end the lJse Thereof as corrosion inhibitor in ail and/or has production ~e~hnol~gy The inventian relates to ammonium salts of alkenyl :>uccinic half-amides and to the use thereof as corrosion inhibitors in oil andlor gas production tech-nology to combat corrosion by media containing CCf2 and HZS and possibly elemental sulfur.
In the production of petroleum and natural gas there usually occurs an oil/water or gas/water mixture which in the case of oil may contain up to about 98% of water.
,° The salinity of the entrained water may be extremely low or conversely, the water may comprise a saturated salt solution. HZS and/or C02 are also present.
The combination of HZS and/or COZ and the water has a strong corrosive ,5 action on metals used in petroleum and natural gas plants. This action is intensified by the presence of elemental sulfur.
It is common practice to inject a solution or dispersion of corrosion inhibitor into the corrosive medium to be handled in the production, transport aad z° storage of petroleum or natural gas. By this means the surface of the metals contacted by the medium is coated with a protective film.
Hitherto, certain imidazoline salts have been proposed for this purpose (cf.
EP 0,065,191 and EP 0,103,737), but these have an unsatisfactory z5 anticorrosive effect against C02 and/or hlzS, especially in the presence of elemental sulfur, as discussed in Environment Treatment ~ Control, Feb.
1990, pp. 43 to 52.
Neither do amine salts of maleamide acids, as described in ~P 0,106,234, 3° possess adequate anticorrosive properties for this purpose.
Oil-soluble amidoamine salts of alkenylsuccinic acids and the use thereof as corrosion inhibitors in water-in-oil emulsions such as occur in oil production are described in EP 0, 359, 043.
~IVater-soluble alkanolamine salts of alkenyisuccinic acids, described in DE
~~~~ AKTIEN~ESELLSCHAFT 2 O.Z, ooso/42171 2,943,963-C2 as being effective as corrosion inhibitors in metal working, also show inadequate anticorrosive action in the systems under consideration here.
It is thus an object of the invention to provide improved, preferably water-soluble inhibitors for use in corrosive media such as occur in petroleum and/or natural gas production, to counteract the corrosive action of CrJ~
and/or H2S, especially when elemental sulfur is present.
,o We have now found that ammonium salts of alkenylsuccinic half-amides of formula (I) below o R~ C-O~A~-H
NCH/ (I) ,s /CH ~
R~ C=0 I
X
in which ZU
R~ denotes H or a Ce-C~~-aikenyl radial, provided that the radicals R' are not both H or both Cg-C~e-alkenyl, X denotes 'a group of the formula -i~HR2 or -fVR2R3, in which R2 and R3 denote C~-CB-alkyl, cycloalkyi or a heterocyclic ring attached to the nitrogen atom via an alkylene chain, and A denotes XH or a different amine of the formula Rn-~ /
ERs in which R4, R5 and Rg independently denote H, C~-Cs-alkyl (in which case R5 and R6 may together form a heterocyclic ring enclosing the nitrogen atom), C~-Cao-hydroxyaikyl or b --~(CH2)~-~N--~(CH2)~-~1H2 , R~
in which R~ denotes H or C~-C3-alkyl, n is an integer from 2 to 4, and m is an integer from 1 to 5, are particularly well suited for use as water-soluble corrosion inhibitors in oil and/or gas production plants.
A particularly suitable representative of the group X is a group of the formula (1l> below H
--N\ / (CH2)r \
(CH2)Q--N~ ~Y (1l), (CH2)p in which q is an integer from 1 to 4, r and p are independently 1 or 2, and Y denotes CRa2, NR$ (where R$ is H or C~-C3-alkyl), O or S.
The present invention also concerns a method of inhibiting corrosion in metals which are in contact with corrosive 20 oil/water or gas/water mixtures found in the production, transport and storage of petroleum and natural gas which comprises: injecting into the corrosive mixture a corrosion inhibiting amount of an ammonium salt of an alkenyl succinic half amide of the formula (I) as defined below, R ~ /C-O~A~-H
i H (I) /CH ~
R~ C=0 X
a in which:
Rl denote; H or_ a C6--c~'1g-alkenyl radical, provided that the radicals R~- :ire not both H or both C6-Cl0-alkenyl, X denotes a grc.-~.y> of t:he formula ( I I ) H
-i~J~ (CH2)r v (CH2)q ~~~, j Y ( I I ), (CH2)p in which q is a.n integer from 1 to 4, r and p are independently J cr ?, and Y denotes CR8~, NR8 (where R8 is F~ or C~_-C j--alkyl) , O or S, and A denotes XH or a d.i.ff_erent amine of t-me formula:
R4-N ,, ,,~Rs in which:
R4, R-'' and R6 independe~zt'_y denote H C1-C6-alkyl (in which case R5 <:~n.d RE~ may toger_iner form a heterocyclic ring including the nit:rc~g~n atone to which they are connected) , Cl--':1,,~-iaydro~:ya:lk:~,r:l- or ..-~-ICH2)n~(CH2)n.-NH2 in which R~ der~ot--cps H c>r ~l--C'_s--a~~.kyl, n is an integer from .L to 4, and m is an inl~ege.r ,=rom 1 to I.
It is part:~cularly adlrantagec~Lr~~ whc_n the group X or the above formLa=La ( T ) i- a rad:icai c>f fo:rrnula ( I I I ) below 3b H
CH2--~H2--~l\ ~N H ( I I I ).
The counterion A°-H is derived either from the amine XH used to form the half-amide or from a different amine of the formula R4-N.
.v Rs ~U
in which R4, R' and Rs have the meanings stated above. Such amines are NH3 or primary, secondary, ar tertiary amines, eg butylamine or dibutylamine, or alkanolamines, eg ethanolamine, diethanolamine, or triethanolamine, or they are polyamines such as diethylenetriamine or dipropylenetriamine.
The alkenylsuccinic amides forming the basis of the salts of the invention are obtained by the following method:
,.' ,r ~~SF AKTIENLiESELLSCHAFT n O.Z, ooso/n2171 1. The endothermic reaction, known per se, between malefic anhydride and the appropriate olefin is carried out at a temperature of from 150° to 250°C under standard pressure conditions or at a temperature of from 150° to 300°C in an autoclave das described in, say, DE A 3, 411, 53 ~ ) and 2. the alkenylsuccinic anhydride thus obtained is reacted with the amine XH
to form the aikenylsuccinic half-amide at a temperature of from 50° to 150°C, preferably from 50° to 120°C, for example in substance or in an ,o aromatic solvent.
The amide/ammonium salts of the invention are obtained therefrom by reaction with the amines A, preferably also at a temperature of from 50° to 120°C. When the same amine components are used for XH and A, the ,3 preparation of the amide/ammonium salt may be effected directly by reacting the alkenylsuccinic anhydride with the amine in a ratio of 1:2.
Particularly noteworthy examples of amines XH are aminoalkylpiperazines and aminoalkylmorpholines, for example aminoethylpiperazine.
2a The inhibitors thus obtained exhibit excellent anticorrosive action against HZS
and COa, and in particular, no impairment of this action is caused by the presence of elemental sulfur.
25 The efificacy of the inhibitors, particularly in the presence of elemental sulfur, can be increased by formulating the products with surface-active substances.
Suitable dispersing agents are: low molecular-weight or polymeric anionic 3o surfactants and dispersing agents, particularly alkylsuffonic acids, alkylarylsul fonic acids, arylsulfonic acids, and the salts thereof.
The corrosion inhibitors of the invention are used in amounts varying from 3 to 1000 ppm depending on the composition of the corrosive modium. To 3s combat corrosion by COx or C02/H2S only, the addition of inhibitor formula-tion is preferably from 5 to 50 ppm, and in the presence of elemental sulfur it is preferably from 100 to 300 ppm.
The invention is illustrated by the following Examples.
;p~ 20~~~~Q
~~~F AKTIENOESELLSCHAFT 5 O.Z.0050/42171 1. Ammonium salt synthesis Example 1 2.3 g of phenothiazine were added to a reaction mixture o~f eguimolar amounts of tetrameric propylene (463 g) and malefic anhydride (269.5 g), and the whole was stirred at a temperature of from 180° to 200°C
over a period of from 25 to 30 hours. Unconverted educts were then distilled off at 175°C under a high vacuum.
,0 A mixture of 342 g of the resulting alkenylsuccinic anhydride and 400 mi of xylene was heated to 80°C, and 368 g of aminoethylpiperazine were added dropwise at this temperature. Stirring was continued 'for 3 hours at the same temperature, and a portion of the solvent was removed under a water jet ,5 vacuum. There was obtained a black viscous product in a yield of 608 g and having a content of 85% of active ingredient.
The tetrameric propylene used was the C12 cut from the olefin oligomer-ization.
z0 as Composition (GC/MS analysis): C9 0.5%; Clo 5.8%; C11 20.7%; C12 70.9%;
C13 2.1 %.
The composition and isomer ratio may vary slightly from batch to batch.
The IR spectrum clearly indicates that the reaction product obtained from the alkenylsuccinic anhydride and aminoethylpiperazine is an ammonium salt of the alkenylsuccinic half-amide, since it shows both characteristic amide bands and -C02 bands. Imide formation is also indicated.
Characteristic IR bands:
Amide: 1680 to 1630 and '1570 to 1515 cm~l C00-: 1610 to 1550 cm°1 Imide: approx. 1770 to approx. 1700 cm-' .
The ammonium salts of the invention can be isolated from the reaction solution by conventional means.
Exarr~pBe 2 387 g of trimeric butylene (prepared by trimerization of n-butane) and 225 g b II~~~~AKTIENQESELLSCHAFT ' 6 ~',~ O.Z.005p/~2~~~
of malefic anhydride were placed in an autoclave. A nitrogen pressure of 5 bar was established, and the reaction mixture was stirred for 10 hours at a temperature of 200°C.
595 g of the reaction product were dissolved in 300 ml of xylene, and the solution was heated to 80°C. 578 g of aminoethyipiperazine were added dropwise at this temperature. The reaction mixture was stirred for 4 hours at the same temperature, after which a portion of the solvent was removed under a water jet vacuum to give the desired corrosion inhibitor as a dark ,° colored viscous oil.
Example 3 Example 2 was repeated except that a linear C»-olefin was used in place ,5 of trimeric butylene.
Exxaraiple ~
An alkenyisuccinic anhydride was prepared frorr~ trimeric butylene and Zp malefic anhydride as described in Example 2. Unconverted olefin and anhydride were removed at 100°C/30 mbar.
198 g (0.75 mole) of this product were dissolved in xylene, and the solution was heated to 100°C. 97 g (0.75 mole) of aminoethylpiperazine were slowly 25 added dropwise at this temperature. The reaction solution was then stirred for about 5 hours at 90-100°C. The solvent was then removed to give 290 g of a black viscous reaction product.
3o In order to neutralize the free carboxyl groups, 101 g (0.2 mole) of this product wore reacted with 26 g (0.2 mote) of diethylenetriamine in xylene at 80°C. The product was concentrated in a rotary evaporator to about 83%
to give the corrosion inhibitor of the invention in the form of a black viscous oil.
2. Examples of application The inhibitor formulations were tested dynamically using the "wheel-test"
described, for example, in EP A 0,359,048, which is a common method of 4° testing corrosion inhibitors in petroleum and natural gas production plants.
The test coupons were large steel plates of ST 37 which had previously been thoroughly ground with emery, degreased with toluene, and weighed.
I~~~FAKTIENQESELLSCHAFT 7 0.2.0050/42171 The coupons were then placed in the corrosive medium and were agitated therein for 16 hours at 80°C (40 rpm via a shaft coupled to rotate the test vessel). The specimens were then cleaned with an inhibited acid, degreased, dried, and weighed in order to determine the weight loss. The results were compared with reference values obtained in a test carried out without the addition of inhibitor.
,°
The anticorrosive factor Z in percent was calculated from the weighings using the following equation:
z = ~° G G~ x 100 [~o~
where G° is the rate of corrosion without inhibitor and G~ is the rate of corrosion with inhibitor.
The results are listed in the Tables below.
TABLE 1 - Anticorrosive factor Z [%J
Medium:
z 10% white 90% brine (3! NaCI?; and/or H25 spirit, saturated with C02 Saturated with:C02/CO2 CO2/H2S
Inhibitor dosage:3 ppm 7.5 ppm 3 ppm 7.5 ppm Product from Example 1 46 78 68 79 Example 2 51 75 74 80 F.~cample 3 61 64 76 81 Example 4 80 80 b ~~~FAKTIENQESELLSCHAFT 8 - O.Z.0050/421%1 TABI_~ 2 Medium: approx. 6.5 ml of brine saturated with H2S, approx. 193,5 ml of brine saturated with C02 , 0.5 g of ground sulfur Inhibitor dosage:150 ppm Product from Dispersing agent Anticorrosive factor Z L%J
Example 1 - 50 Example 1 10! oiigomeric aryl sulfonate 82 (Tamol 941 Oa) Example 1 15% alkylbenzene sulfonate 78 (ALBS) ,0 Example 2 10% oligomeric aryl sulfonate 85 Example ~ 15% ALBS 78 Example 3 15% ALBS 80 Example 3 10% oligomeric aryl sulfonate 75 Examale 4 15% ALBS 80 ,5 Comparative Examples Medium: approx. 6.5 ml of brine saturated with H2S, approx. 193.5 ml of brine saturated with C02, 0.5 g of ground sulfur Z° Inhibitor dosage: 150 ppm Product Dispersing agent Anticorrosive factor [%7 1. acetate of a long-chain - 17 imidazoline 2. amido-imidazoline plus - 33 Z5 dimerized/trimerized fatty acid 3. amido-imidazoline - 25 4. as for 1 10% oligomeric aryl 0 sulfonate 3° 5. as for 1 15% alkylbenzene 12 sulfonate It can be seen from the above results that the commercially available corrosion inhibitors are distinctly less effective and that the addition of 35 dispersing agents to said prior art corrosion inhibitors has no advantageous effect.
By comparison, the ammonium salts of the invention are found to be highly effective corrosion inhibitors.
Claims (10)
1 . An ammonium salt of an alkenylsuccinic half-amide of formula (I) below in which R1 denotes H or a C6-C18-alkenyl radical, provided that the radicals R1 are not both H or both C6-C18-alkenyl, X denotes a group of the formula (II):
in which q is an integer from 1 to 4, r and p are independently 1 or 2, and Y denotes CR8 2, NR8 (where R8 is H or C1-C3-alkyl), O or S, and A denotes XH or a different amine of the formula in which R4, R5 and R6 independently denote H, C1-C6-alkyl (in which case R5 and R6 may together, form a heterocyclic ring including the nitrogen atom to which they are connected), C1-C10-hydroxyalkyl or in which R7 denotes H or C1-C3-alkyl, n is an integer from 2 to 4, and m is an integer from 1 to 5.
in which q is an integer from 1 to 4, r and p are independently 1 or 2, and Y denotes CR8 2, NR8 (where R8 is H or C1-C3-alkyl), O or S, and A denotes XH or a different amine of the formula in which R4, R5 and R6 independently denote H, C1-C6-alkyl (in which case R5 and R6 may together, form a heterocyclic ring including the nitrogen atom to which they are connected), C1-C10-hydroxyalkyl or in which R7 denotes H or C1-C3-alkyl, n is an integer from 2 to 4, and m is an integer from 1 to 5.
2. An ammonium salt of the general formula (I) as set forth in claim 1, in which:
X denotes a group of formula (III)
X denotes a group of formula (III)
3. A process for the preparation of an ammonium salt of an alkenyl-succinic half-amide as claimed in claim 1, wherein a) a C6-C18-alkene is reacted in an endothermic reaction with maleic anhydride at a temperature of from 150° to 250°C under standard pressure conditions or at a temperature of from 150° to 300°C in an autoclave, b) the resulting alkenylsuccinic anhydride is reacted with an amine XH at a temperature of from 50° to 150°C; over a period of from 1 to 8 hours to form an alkenylsuccinic half-amide, and the alkenylsuccinic half-amide is neutralized with an amine A.
4. An anticorrosive agent containing an ammonium salt as claimed in claim 1 and a dispersing agent.
5. An anticorrosive agent as claimed in claim 4 wherein the dispersing agent contained therein is a low molecular-weight or polymeric anionic surfactant, selected from the group consisting of an alkylsulfonic acid, alkylaryl-sulfonic acid, an arylsulfonic acid and a salt of said acids.
6. An anticorrosive formulation as defined in claim 4, where X denotes a group of the formula below:
7. A method of inhibiting corrosion in metals which are in contact with corrosive oil/water or gas/water mixtures found in the production, transport and storage of petroleum and natural gas which comprises: injecting into the corrosive mixture a corrosion inhibiting amount of an ammonium salt of an alkenyl succinic half amide of the formula (I) as defined below, in which:
R1 denotes H or a C6-C18-alkenyl radical, provided that the radicals R1 are not both H or both C6-C10-alkenyl, X denotes a group of the formula (II):
in which q is an integer from 1 to 4, r and p are independently 1 or 2, and y denotes CR8 2, NR8 (where R8 is H or C1-C3-alkyl), O or S, and A denotes XH or a different amine of the formula:
in which R4, R5 and R6 independently denote H, C1-C6-alkyl (in which case R5 and R6 may together form a heterocyclic ring including the nitrogen atom to which they are connected), C1-C10-hydroxyalkyl or in which R7 denotes H or C1-C3-alkyl, n is an integer from 1 to 4, and m is an integer from 1 to 5.
R1 denotes H or a C6-C18-alkenyl radical, provided that the radicals R1 are not both H or both C6-C10-alkenyl, X denotes a group of the formula (II):
in which q is an integer from 1 to 4, r and p are independently 1 or 2, and y denotes CR8 2, NR8 (where R8 is H or C1-C3-alkyl), O or S, and A denotes XH or a different amine of the formula:
in which R4, R5 and R6 independently denote H, C1-C6-alkyl (in which case R5 and R6 may together form a heterocyclic ring including the nitrogen atom to which they are connected), C1-C10-hydroxyalkyl or in which R7 denotes H or C1-C3-alkyl, n is an integer from 1 to 4, and m is an integer from 1 to 5.
8. A method of inhibiting corrosion in metals which are in contact with corrosive oil/water or gas/water mixtures found in the production, transport and storage of petroleum and natural gas which comprises: injecting into the corrosive mixture a corrosion inhibiting amount of an ammonium salt of the formula (I) as defined in claim 7, where X denotes a group of the formula (III);
9. A method as defined in claim 7, wherein the corrosive medium contains CO2 and/or H2S.
10. A method as claimed in claim 9, wherein the corrosive medium also contains elemental sulfur.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4103262A DE4103262A1 (en) | 1991-02-04 | 1991-02-04 | ALMONIUM SALTS OF ALKENYLSBERSTIC ACID HALBAMIDES AND THEIR USE AS CORROSION INHIBITORS IN OIL AND / OR GAS PRODUCTION |
| DEP4103262.4 | 1991-02-04 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2060580A1 CA2060580A1 (en) | 1992-08-05 |
| CA2060580C true CA2060580C (en) | 2004-04-20 |
Family
ID=6424313
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002060580A Expired - Lifetime CA2060580C (en) | 1991-02-04 | 1992-02-03 | Ammonium salt of an alkenylsuccinic half-amide and the use thereof as corrosion inhibitor in oil and/or gas production technology |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0498178B1 (en) |
| CA (1) | CA2060580C (en) |
| DE (2) | DE4103262A1 (en) |
| NO (1) | NO302171B1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102471899B (en) | 2009-07-03 | 2015-05-27 | 阿克佐诺贝尔化学国际公司 | Polymeric corrosion inhibitors |
| AU2011298474B2 (en) | 2010-08-30 | 2014-01-16 | Akzo Nobel Chemicals International B.V. | Use of polyester polyamine and polyester polyquaternary ammonium compounds as corrosion inhibitors |
| US9493715B2 (en) | 2012-05-10 | 2016-11-15 | General Electric Company | Compounds and methods for inhibiting corrosion in hydrocarbon processing units |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2943963A1 (en) * | 1979-10-31 | 1981-05-14 | Basf Ag, 6700 Ludwigshafen | Iron corrosion inhibition - with aq. system contg. alkanolamine salt(s) of alkenyl succinic acid(s) |
| DE3119376A1 (en) * | 1981-05-15 | 1982-12-02 | Basf Ag, 6700 Ludwigshafen | INHIBITORS AGAINST THE CORROSION OF H (DOWN ARROW) 2 (DOWN ARROW) S AND CO (DOWN ARROW) 2 (DOWN ARROW) IN WATER-IN-OIL EMULSIONS |
| US4557838A (en) * | 1982-04-08 | 1985-12-10 | Air Products And Chemicals, Inc. | Inhibiting acid corrosion of metals |
| DE3237109A1 (en) * | 1982-10-07 | 1984-04-12 | Basf Ag, 6700 Ludwigshafen | USE OF AMINE SALTS OF MALEINAMID ACIDS AS INHIBITORS AGAINST THE CORROSION OF CO (DOWN ARROW) 2 (DOWN ARROW) AND H (DOWN ARROW) 2 (DOWN ARROW) S IN WATER-IN-OIL EMULSIONS |
| DE3300874A1 (en) * | 1983-01-13 | 1984-07-19 | Henkel KGaA, 4000 Düsseldorf | Succinic acid derivatives as corrosion protection agents |
| DE3830068A1 (en) * | 1988-09-03 | 1990-04-05 | Hoechst Ag | AMIDOAMINE SALTS OF ALKENYLSBERSTEINSEUR DERIVATIVES, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS CORROSION INHIBITORS |
-
1991
- 1991-02-04 DE DE4103262A patent/DE4103262A1/en not_active Withdrawn
-
1992
- 1992-01-16 EP EP92100625A patent/EP0498178B1/en not_active Expired - Lifetime
- 1992-01-16 DE DE59209016T patent/DE59209016D1/en not_active Expired - Lifetime
- 1992-02-03 NO NO920440A patent/NO302171B1/en not_active IP Right Cessation
- 1992-02-03 CA CA002060580A patent/CA2060580C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| NO920440L (en) | 1992-08-05 |
| DE59209016D1 (en) | 1997-12-18 |
| EP0498178A2 (en) | 1992-08-12 |
| NO302171B1 (en) | 1998-02-02 |
| CA2060580A1 (en) | 1992-08-05 |
| DE4103262A1 (en) | 1992-08-13 |
| EP0498178A3 (en) | 1993-03-03 |
| EP0498178B1 (en) | 1997-11-12 |
| NO920440D0 (en) | 1992-02-03 |
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