WO1999039025A1 - Ecologically compatible carbon corrosion inhibitors of iron - Google Patents

Ecologically compatible carbon corrosion inhibitors of iron Download PDF

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Publication number
WO1999039025A1
WO1999039025A1 PCT/FR1999/000163 FR9900163W WO9939025A1 WO 1999039025 A1 WO1999039025 A1 WO 1999039025A1 FR 9900163 W FR9900163 W FR 9900163W WO 9939025 A1 WO9939025 A1 WO 9939025A1
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mercaptoacid
polymethylene
acid
independently
weight
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PCT/FR1999/000163
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French (fr)
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Tong Eak Pou
Stéphane Fouquay
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Ceca
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Priority to AU21676/99A priority Critical patent/AU2167699A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/54—Compositions for in situ inhibition of corrosion in boreholes or wells
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors

Definitions

  • carbon dioxide corrosion In oil and gas production, corrosion due to carbon dioxide, known as carbon dioxide corrosion, occurs at the bottom of wells, where the temperature is generally around 60 ° C or more, in surface pipes and in crude refining facilities. This is usually remedied by the use of corrosion inhibitors based on amine salts, quaternary ammonium salts, imidazolines or phosphoric esters. These compounds are not entirely satisfactory because "ecotoxic.
  • compositions associating a poly ethylene-polyamino-dipropionamide and a mercaptoacid compound; more explicitly, for compositions comprising as active material
  • R4 and R5, together or independently OH, NH 2 , or SH when
  • R 8 H, C ⁇ - ⁇ >
  • R 2 to R5 can be included in an aliphatic cycle
  • R3 and R5 can be included in an aromatic cycle when q-1, A being an acid group COOH, S0 3 H, OS0 3 H, PO 3 H or OPO3H, the weight ratio between the mercaptoacid component (s) and the component (s) dipropionamides being between
  • Polymethylene-polyamino-dipropionamides are easily obtained by condensation of acrylamide on polymethylene-polyamine bases, for example EDA, DETA bases,
  • mercaptoacidic acids for example mercaptoacetic acid HSCH 2 COOH, RN ⁇ [68-11-1], or mercaptopropionic acid HSCH 2 CH 2 COOH, RN ⁇ [107-96-0]
  • the inhibitory compositions of the invention are compositions in which the mercaptoacid components, alone or as a mixture, and dipropionamides are present in weight ratios of 0.3 to 2, but the maximum inhibitory efficacy is found for weight ratios of 0.5 and 1.
  • compositions according to the invention are advantageously presented in the form of aqueous solutions containing 10% - 75% of active material, which are very simply obtained by cold or lukewarm mixing of the constituents. They are also an object of the present invention.
  • the inhibitor compositions according to the invention can be used in continuous injection as well as in sequential treatment. Continuously, the useful dosages are between 3 ppm and 100 ppm expressed by weight of active material, mercaptoacid + dipropionamide relative to the corrosive medium. In sequence treatment, it can be used at a dose of 1% to 10% relative to the carrier fluid, water for example.
  • the invention finds an important application for the protection of steel against CO 2 corrosion in the petroleum production industry.
  • the synergistic compositions of the invention are also satisfactory as inhibitors of hydrosulfuric corrosion of iron.
  • the polymethylene-polyamino-diproprionamide used was dipropionamide based on TETA with the formula NH 2 CO (CH 2 ) 2 NH [(CH 2 ) 2 NH] 3 (CH 2 ) 2 CONH 2
  • the test temperature is 80 ° C.
  • the instantaneous corrosion rate V corr is measured by measurement of polarization resistance, a method well known to those skilled in the art.
  • the mercaptoacetic acid used in the test is thioglycolic acid from Elf atochem.
  • Table 1 gives the values of the corrosion rate of the steel as a function of inhibiting composition (weight compositions, mercaptoacid / dipropionamide weight ratio, pH of the formula).
  • the test compositions are used at the uniform dose of 15 ppm of active material, expressed by weight of all the active components, that is to say mercaptoacetic acid + dipropionamide.
  • Table 1 Residual corrosion rate in the presence of 15 ppm of active ingredients of the formulas studied.
  • Example 1 The operation is carried out according to the procedure described in Example 1.
  • the mercaptoacid used is mercaptopropionic acid from Elf Atochem.
  • Table 2 summarizes the composition information of the inhibitor and the measured corrosion rates.
  • Corrosive medium solution containing 50 g / 1 of NaCl + 0.25 g / 1 of CH3COOH, saturated with C0 2
  • Working temperature 80 ° C
  • White corrosion rate 20 mm / year
  • compositions of the invention lend themselves to formulation in relatively concentrated presentations.
  • compositions 16 and 17 reported in Table 3 with their characteristics of composition and inhibitory efficacy titrate 50% of active material and are fluid solutions.
  • Table 3 gives the compositions and the residual corrosion rates in the presence of 15 ppm activates 50 ppm of new formulas, in the corrosive medium studied at 80 ° C.
  • Corrosive medium solution containing 50 g / 1 of NaCl + 0.25 g / 1 of CH3COOH, saturated with C0 2 Working temperature: 80 ° C
  • the ecotoxicity measurements were carried out on a bacterium (Photobacterium phosphoreum) according to the Microtox test, AFNOR NF T90-320, and on an alga (SJceletonei-ia costatum) according to the ISO / DIS 10253 method.
  • the toxicity according to Microtox is expressed in LC5 0 (lethal concentration in mg / 1 to destroy 50% of the population in 15 minutes); the toxicity according to ISO / DIS 10253 is expressed in CE5 0 (effective concentration in mg / 1 to inhibit the growth of 50% of the population in 72 hours).

Abstract

The invention concerns compositions wherein polymethylene-polyaminodipropionamides associated with mercaptoacids develop remarkable synergy in their function inhibiting carbon corrosion of steel and in their ecological compatibility.

Description

INHIBITEURS DE LA CORROSION CARBONIQUE DU FER ECOCOMPATIBLESCARBONIC CORROSION OF INHIBITORS OF ECOCOMPATIBLE IRON
DOMAINE TECHNIQUE DE L'INVENTION ET ART ANTERIEURTECHNICAL FIELD OF THE INVENTION AND PRIOR ART
Dans la production du pétrole et du gaz, la corrosion due au gaz carbonique, connue sous le nom de corrosion carbonique, a lieu en fond de puits, où la température se situe en général vers 60°C ou plus, dans les canalisations de surface et dans les installations de raffinage du brut. On y remédie habituellement par utilisation d'inhibiteurs de corrosion à base de sels d'aminés, de sels d'ammonium quaternaire , d ' imidazolines ou d ' esters phosphoriques . Ces composés ne sont pas entièrement satisfaisants parce qu» écotoxiques .In oil and gas production, corrosion due to carbon dioxide, known as carbon dioxide corrosion, occurs at the bottom of wells, where the temperature is generally around 60 ° C or more, in surface pipes and in crude refining facilities. This is usually remedied by the use of corrosion inhibitors based on amine salts, quaternary ammonium salts, imidazolines or phosphoric esters. These compounds are not entirely satisfactory because "ecotoxic.
Dans la demande de brevet français n°9701298, il a été proposé d'utiliser les polyméthylène-polyamino- diproprionamides comme inhibiteurs de corrosion non écotoxiques pour l'environnement marin.In French patent application No. 9701298, it has been proposed to use polymethylene-polyamino-diproprionamides as non-ecotoxic corrosion inhibitors for the marine environment.
EXPOSE DE L'INVENTIONSTATEMENT OF THE INVENTION
On vient maintenant de trouver une activité synergique inattendue quant à l'établissement d'une inhibition de la corrosion carbonique du fer dans les milieux aqueux, pour des compositions aqueuses associant un poly éthylène-polyamino- dipropionamide et un composé mercaptoacide ; de façon plus explicite, pour des compositions comportant comme matière activeWe have now just found an unexpected synergistic activity as regards the establishment of an inhibition of carbonic corrosion of iron in aqueous media, for aqueous compositions associating a poly ethylene-polyamino-dipropionamide and a mercaptoacid compound; more explicitly, for compositions comprising as active material
- au moins l'un des polyméthylène-polyaminodipropionamides correspondant à la formule :- at least one of the polymethylene polyaminodipropionamides corresponding to the formula:
H2NCO- (CH2)2-NH-[ (CH2) ~NH - (CH2)2-CONH2 dans laquelle m est un nombre entier pouvant prendre toute valeur de 1 à 4 , qui représente le nombre de maillons polyméthylène-amino -(CH2)n-NH- , n pouvant avoir dans chaque maillon polyméthylène-amino une valeur entière de 2 à 6, - au moins un mercaptoacide répondant à la formule généraleH 2 NCO- (CH 2 ) 2 -NH- [(CH 2 ) ~ NH - (CH 2 ) 2 -CONH 2 in which m is an integer which can take any value from 1 to 4, which represents the number of polymethylene-amino links - (CH 2 ) n -NH-, n which can have in each polymethylene-amino link an integer value of 2 to 6, - at least one mercaptoacid corresponding to the general formula
R2 4 R 2 4
R-, +C- CΑ 1 Ll Jq |R-, + C- CΑ 1 L l J q |
R3 R5 avec q = 0 à 3, Rx≈H ou SH, R 3 R 5 with q = 0 to 3, Rx≈H or SH,
R2 et R3, ensemble ou indépendamment = C3.-4, CON(Rg) (R7) ,R 2 and R 3 , together or independently = C 3. -4, CON (Rg) (R 7 ),
COOR9 ,COOR 9 ,
R4 et R5, ensemble ou indépendamment = OH, NH2, ou SH quandR4 and R5, together or independently = OH, NH 2 , or SH when
Ri≠SH, Rg et R7, ensemble ou indépendamment = H, C1-.4,Ri ≠ SH, Rg and R 7 , together or independently = H, C1-. 4 ,
R8 = H, Cλ- β >R 8 = H, C λ - β>
R2 à R5 pouvant être inclus dans un cycle aliphatique,R 2 to R5 can be included in an aliphatic cycle,
R3 et R5 pouvant être inclus dans un cycle aromatique lorsque q-1, A étant un groupe acide COOH, S03H, OS03H, PO3H ou OPO3H, le rapport pondéral entre le ou les composants mercaptoacides et le ou les composants dipropionamides étant compris entreR3 and R5 can be included in an aromatic cycle when q-1, A being an acid group COOH, S0 3 H, OS0 3 H, PO 3 H or OPO3H, the weight ratio between the mercaptoacid component (s) and the component (s) dipropionamides being between
0,3 et 2.0.3 and 2.
Les polyméthylène-polyamino-dipropionamides s'obtiennent aisément par condensation d'acrylamide sur des bases polyméthylène-polyamines, par exemple les bases EDA, DETA,Polymethylene-polyamino-dipropionamides are easily obtained by condensation of acrylamide on polymethylene-polyamine bases, for example EDA, DETA bases,
TETA, TEPA, HEPA en série ethylènimine, les bases PDA, DPTA (Norspermidine) en série propylèneimine, ou encore des composés hybrides éthylène/propylèneimine .TETA, TEPA, HEPA in ethylenimine series, PDA, DPTA (Norspermidine) bases in propyleneimine series, or hybrid ethylene / propyleneimine compounds.
On les caractérise parfaitement par spectrographie RMN. Ils offrent déjà en eux-mêmes une très faible écotoxicité marine (50 à 100 ppm sur Skeletonema costatum) . Les mercaptoacides utiles pour l'invention, tels que décrits plus haut, sont très généralement des produits connus .They are perfectly characterized by NMR spectrography. They already offer in themselves a very low marine ecotoxicity (50 to 100 ppm on Skeletonema costatum). The mercapto acids useful for the invention, as described above, are very generally known products.
On préfère les mercaptoacides carboxyliques, par exemple l'acide mercaptoacetique HSCH2COOH, RN≈ [68-11-1] , ou l'acide mercaptopropionique HSCH2CH2COOH, RN≈ [107-96-0]Preferred are mercaptoacidic acids, for example mercaptoacetic acid HSCH 2 COOH, RN≈ [68-11-1], or mercaptopropionic acid HSCH 2 CH 2 COOH, RN≈ [107-96-0]
Les compositions inhibitrices de l'invention sont des compositions dans lesquelles les composants mercaptoacides, seuls ou en mélange, et dipropionamides sont présents dans des rapports pondéraux de 0,3 à 2, mais le maximum d'efficacité inhibitrice se trouve pour des rapports pondéraux de 0,5 et 1.The inhibitory compositions of the invention are compositions in which the mercaptoacid components, alone or as a mixture, and dipropionamides are present in weight ratios of 0.3 to 2, but the maximum inhibitory efficacy is found for weight ratios of 0.5 and 1.
Mais ce qui est encore plus étonnant, c'est que cette synergie se manifeste également au niveau de 1 ' écotoxicité, les compositions synergiques de 1 ' invention se révélant de façon inattendue beaucoup moins écotoxiques que chacun de leurs composants pris isolément .But what is even more astonishing is that this synergy also manifests itself at the level of ecotoxicity, the synergistic compositions of the invention unexpectedly proving to be much less ecotoxic than each of their components taken in isolation.
Les compositions selon l'invention sont avantageusement présentées sous forme de solutions aqueuses à 10 % - 75 % de matière active, qu'on obtient très simplement par mélange à froid ou à tiède des constituants. Elles sont également un objet de la présente invention.The compositions according to the invention are advantageously presented in the form of aqueous solutions containing 10% - 75% of active material, which are very simply obtained by cold or lukewarm mixing of the constituents. They are also an object of the present invention.
Les compositions inhibitrices selon l'invention peuvent être utilisées en injection en continu aussi bien qu'en traitement séquence. En continu, les dosages utiles sont compris entre 3 ppm et 100 ppm exprimés poids de matière active, mercaptoacide + dipropionamide par rapport au milieu corrosif. En traitement séquence, on peut l'utiliser à la dose de 1 % à 10 % par rapport au fluide porteur, l'eau par exemple . L'invention trouve une application importante pour la protection de 1 ' acier contre la corrosion C02 dans l'industrie de la production pétrolière. Les compositions synergiques de 1 ' invention donnent également satisfaction comme inhibiteurs de la corrosion suifhydrique du fer.The inhibitor compositions according to the invention can be used in continuous injection as well as in sequential treatment. Continuously, the useful dosages are between 3 ppm and 100 ppm expressed by weight of active material, mercaptoacid + dipropionamide relative to the corrosive medium. In sequence treatment, it can be used at a dose of 1% to 10% relative to the carrier fluid, water for example. The invention finds an important application for the protection of steel against CO 2 corrosion in the petroleum production industry. The synergistic compositions of the invention are also satisfactory as inhibitors of hydrosulfuric corrosion of iron.
Les exemples qui suivent, sont destinés à mieux faire comprendre 1 ' invention et ses avantages .The examples which follow are intended to better understand the invention and its advantages.
EXEMPLESEXAMPLES
Dans les exemples, le polyméthylène-polyamino- diproprionamide utilisé a été le dipropionamide sur base TETA de formule NH2CO(CH2)2NH [(CH2)2NH]3 (CH2)2CONH2 In the examples, the polymethylene-polyamino-diproprionamide used was dipropionamide based on TETA with the formula NH 2 CO (CH 2 ) 2 NH [(CH 2 ) 2 NH] 3 (CH 2 ) 2 CONH 2
(C12H28Ng02 . M = 288,39 g . mol-1), dont les caractéristiques RMN sont rapportées au tableau ci-joint.(C 12 H 28 Ng0 2. M = 288.39 g. Mol -1 ), the NMR characteristics of which are given in the attached table.
Tableau des caractéristiques RMN du dipropionamideTable of NMR characteristics of dipropionamide
NH2CO(CH2)2NH [(CH2)2NH]3 (CH2)2CONH2 NH 2 CO (CH 2 ) 2 NH [(CH 2 ) 2 NH] 3 (CH 2 ) 2 CONH 2
1 2 3 4 5 6 6 5 4 3 2 11 2 3 4 5 6 6 5 4 3 2 1
H2N CO CH2 CH2 NH CH2 CH2 NH CH2 CH2 NH CH2 CH2 NH CH2 CH2 co NH2
Figure imgf000006_0001
H2N CO CH2 CH2 NH CH2 CH2 NH CH2 CH2 NH CH2 CH2 NH CH2 CH2 co NH2
Figure imgf000006_0001
!H RMN (D20) : 2,34 (t, 4H, H2) ; 2,58 (s, 12H, H4 à Hg) ; 2,73 (t, 4H, H3) . 13C RMN (D20) : 36,7 (C2) ; 46,7 (C3) ; 49,6 (m , C à C ) ; 179,6 (Ci) .! H NMR (D 2 O): 2.34 (t, 4H, H 2 ); 2.58 (s, 12H, H 4 to Hg); 2.73 (t, 4H, H 3 ). 13 C NMR (D 2 0): 36.7 (C 2 ); 46.7 (C 3 ); 49.6 (m, C to C); 179.6 (Ci).
EXEMPLE 1 : propriétés inhibitrices de l'association polyami- nodipropionamide - acide mercaptoacetique Pour évaluer l'efficacité inhibitrice de corrosion des produits mis en oeuvre pour réduire la corrosion en milieu saturé en gaz carbonique, la procédure expérimentale utilisée a été la suivante. Comme milieu corrosif, on utilise une solution de type NACE contenant 50 g/1 de NaCl et de 0,25 g/1 d'acide acétique saturée par barbotage en continu de C02.EXAMPLE 1 Inhibitory Properties of the Polyamino-propionamide-Mercaptoacetic Acid Association To evaluate the corrosion inhibitory efficacy of the products used to reduce corrosion in a medium saturated with carbon dioxide, the experimental procedure used was as follows. As the corrosive medium, a NACE type solution is used containing 50 g / l of NaCl and 0.25 g / l of acetic acid saturated by continuous bubbling of CO 2 .
On opère dans une cellule de Pyrex thermostatée de 600 ml comportant outre une entrée et une sortie de gaz, trois électrodes assujetties à la cellule par des rodages. Elles sont composées d'une électrode de travail en acier au carbone dont la surface de contact avec la solution corrosive est de 1 cm2, d'une électrode de référence (électrode au calomel saturé) et d'une contre électrode en platine à très grande surface en contact avec la solution corrosive. On place dans la cellule 500 ml de la solution corrosive, on introduit ensuite la contre électrode et 1 ' électrode de référence. On désaère la solution par barbotage d'azote pendant une heure et on la sature en C02 par barbotage par ce gaz pendant au moins une heure supplémentaire. Pour bien assurer la saturation en C02, on laisse barboter ce gaz pendant toute la durée de 1 ' expérience .We operate in a 600 ml thermostated Pyrex cell comprising, in addition to a gas inlet and outlet, three electrodes secured to the cell by lapping. They are composed of a carbon steel working electrode whose contact surface with the corrosive solution is 1 cm 2 , a reference electrode (saturated calomel electrode) and a platinum counter electrode with very large surface in contact with the corrosive solution. 500 ml of the corrosive solution are placed in the cell, the counter electrode and the reference electrode are then introduced. The solution is deaerated by bubbling nitrogen for one hour and is saturated with CO 2 by bubbling with this gas for at least one additional hour. To ensure good saturation with C0 2 , this gas is allowed to bubble for the duration of the experiment.
La température de l'essai est de 80°C.The test temperature is 80 ° C.
On mesure la vitesse de corrosion instantanée Vcorr par mesure de résistance de polarisation, méthode bien connue de l'homme du métier. L'acide mercaptoacetique utilisé dans l'essai est l'acide thioglycolique de Elf atochem. Le tableau 1 donne les valeurs de la vitesse de corrosion de l'acier en fonction de composition inhibitrice (compositions pondérales, rapport pondéral mercaptoacide/dipropionamide, pH de la formule) . Les compositions d'essai sont utilisées à la dose uniforme de 15 ppm en matière active, exprimées en poids de l'ensemble des composants actifs, c'est-à-dire acide mercaptoacetique + dipropionamide . Tableau 1 Vitesse de corrosion résiduelle en présence de 15 ppm de matières actives des formules étudiées.The instantaneous corrosion rate V corr is measured by measurement of polarization resistance, a method well known to those skilled in the art. The mercaptoacetic acid used in the test is thioglycolic acid from Elf atochem. Table 1 gives the values of the corrosion rate of the steel as a function of inhibiting composition (weight compositions, mercaptoacid / dipropionamide weight ratio, pH of the formula). The test compositions are used at the uniform dose of 15 ppm of active material, expressed by weight of all the active components, that is to say mercaptoacetic acid + dipropionamide. Table 1 Residual corrosion rate in the presence of 15 ppm of active ingredients of the formulas studied.
Milieu corrosif : Solution contenant 50 g/1 de NaCl + 0,25 g/1 de CH3COOH saturé en C0 Température de travail : 80°C Vitesse de corrosion du blanc = 20 mm/anCorrosive medium: Solution containing 50 g / 1 of NaCl + 0.25 g / 1 of CH3COOH saturated with C0 Working temperature: 80 ° C White corrosion rate = 20 mm / year
Formule N° 1 2 3 4 5 6 7 8Formula N ° 1 2 3 4 5 6 7 8
Acide 30 17,5 16 15 6,85 4,5 1,45 ι.Hrra ϋ--aœt-ιqueAcid 30 17.5 16 15 6.85 4.5 1.45 ι.Hrra ϋ - aœt-ιque
Dipropionamide 12,5 14 15 16,45 16,85 17,39 30Dipropionamide 12.5 14 15 16.45 16.85 17.39 30
Eau 70 70 70 70 76,70 78,65 81,16 70Water 70 70 70 70 76.70 78.65 81.16 70
pH 2 3,39 4,77 6,49 7,6 8,7 9,25 10,4pH 2 3.39 4.77 6.49 7.6 8.7 9.25 10.4
Rapport 1,4 1,42 1 0,42 0,27 0,08 pondéralRatio 1.4 1.42 1 0.42 0.27 0.08 weight
Acide/BaseAcid / Base
Vitesse de 11 6,5 4,7 4,5 5 6,1 5,6 9,5 corrosionSpeed of 11 6.5 4.7 4.5 5 6.1 5.6 9.5 corrosion
(mm/an)
Figure imgf000008_0001
(mm / year)
Figure imgf000008_0001
On remarque plus particulièrement la formule n°4, dont le rapport pondéral acide/base des 15 ppm de sa matière active est égal à 1 et qui permet de réduire la vitesse de corrosion résiduelle à 4,5 mm/an. EXEMPLE 2 : Propriétés inhibitrices de l'association polyméthylène-polyamino-diproprionamide - acide mercapto- propioniqueWe notice more particularly formula n ° 4, whose acid / base weight ratio of 15 ppm of its active material is equal to 1 and which makes it possible to reduce the rate of residual corrosion to 4.5 mm / year. EXAMPLE 2 Inhibitory Properties of the Polymethylene-Polyamino-Diproprionamide-Mercaptopropionic Acid Association
On opère selon le mode opératoire décrit dans 1 ' exemple 1. Dans le présent exemple, le mercaptoacide utilisé est l'acide mercaptopropionique d'Elf Atochem.The operation is carried out according to the procedure described in Example 1. In the present example, the mercaptoacid used is mercaptopropionic acid from Elf Atochem.
Le tableau 2 récapitule les informations de composition de 1 ' inhibiteur et les vitesses de corrosion mesurées .Table 2 summarizes the composition information of the inhibitor and the measured corrosion rates.
Tableau 2 Vitesse de corrosion résiduelle en présence de 15 ppm de matière active des formules étudiées.Table 2 Residual corrosion rate in the presence of 15 ppm of active ingredient of the formulas studied.
Milieu corrosif : solution contenant 50 g/1 de NaCl + 0.25 g/1 de CH3COOH, saturée en C02 Température de travail : 80°C Vitesse de corrosion du blanc = 20 mm/anCorrosive medium: solution containing 50 g / 1 of NaCl + 0.25 g / 1 of CH3COOH, saturated with C0 2 Working temperature: 80 ° C White corrosion rate = 20 mm / year
Formule n° 9 10 11 12 13 14 15Formula n ° 9 10 11 12 13 14 15
Acide mercapto30 39,28 24,78 8,10 5,50 2,30 propioniqueMercapto30 acid 39.28 24.78 8.10 5.50 2.30 propionic
Dipropionamide 10,72 13,27 16,20 16,70 17,25 30Dipropionamide 10.72 13.27 16.20 16.70 17.25 30
Eau 70 50 61,95 75,70 77,80 80,45 70Water 70 50 61.95 75.70 77.80 80.45 70
pH 2 3,83 5,27 6,73 8 9,33 10,4pH 2 3.83 5.27 6.73 8 9.33 10.4
Rapport pondéral 3,66 1,87 0,5 0,33 0,13 Acide/BaseWeight ratio 3.66 1.87 0.5 0.33 0.13 Acid / Base
Vitesse de 10 5,5 5,8 4,5 5 5,5 9,5 corrosion (mm/an)
Figure imgf000009_0001
On remarque plus particulièrement la formule n° 12, à laquelle correspond la vitesse de corrosion résiduelle la plus faible (4,5 mm/an) .Speed of 10 5.5 5.8 4.5 5 5.5 9.5 corrosion (mm / year)
Figure imgf000009_0001
We notice more particularly formula n ° 12, which corresponds to the lowest residual corrosion rate (4.5 mm / year).
EXEMPLE 3 : Formules concentréesEXAMPLE 3 Concentrated formulas
Les compositions de l'invention se prêtent à la formulation sous des présentations relativement concentrées. Les compositions 16 et 17 rapportées au tableau 3 avec leurs caractéristiques de composition et d'efficacité inhibitrice titrent 50% de matière active et sont des solutions fluides.The compositions of the invention lend themselves to formulation in relatively concentrated presentations. The compositions 16 and 17 reported in Table 3 with their characteristics of composition and inhibitory efficacy titrate 50% of active material and are fluid solutions.
Le tableau 3 donne les compositions et les vitesses de corrosion résiduelle en présence de 15 ppm active 50 ppm de nouvelles formules, dans le milieu corrosif étudié à 80°C.Table 3 gives the compositions and the residual corrosion rates in the presence of 15 ppm activates 50 ppm of new formulas, in the corrosive medium studied at 80 ° C.
Tableau 3 Vitesse de corrosion résiduelle en présence de 25 ppm de matière active des formules étudiées.Table 3 Residual corrosion rate in the presence of 25 ppm of active ingredient of the formulas studied.
Milieu corrosif : solution contenant 50 g/1 de NaCl + 0.25 g/1 de CH3COOH, saturée en C02 Température de travail : 80°CCorrosive medium: solution containing 50 g / 1 of NaCl + 0.25 g / 1 of CH3COOH, saturated with C0 2 Working temperature: 80 ° C
Formule n° 16 n° 17Formula n ° 16 n ° 17
Acide mercaptoacetique 25Mercaptoacetic acid 25
Acide mercaptopropionique 17,5Mercaptopropionic acid 17.5
Dipropionamide 25 32,5Dipropionamide 25 32.5
Eau 50 50Water 50 50
Rapport Acide/Base 1 0,54Acid / Base Ratio 1 0.54
Vitesse de corrosion 1,8 1,0 résiduelle (mm/an)
Figure imgf000010_0001
EXEMPLE 4 : ECOTOXICITECorrosion rate 1.8 1.0 residual (mm / year)
Figure imgf000010_0001
EXAMPLE 4: ECOTOXICITY
Les mesures d' écotoxicité ont été réalisées sur une bactérie ( Photobacterium phosphoreum) selon le test Microtox, AFNOR NF T90-320, et sur une algue (SJceletonei-ia costatum) selon la méthode ISO/DIS 10253. La toxicité selon Microtox est exprimée en CL50 (concentration létale en mg/1 pour détruire 50% de la population en 15 minutes) ; la toxicité selon ISO/DIS 10253 est exprimée en CE50 (concentration effective en mg/1 pour inhiber la croissance de 50 % de la population en 72 heures) .The ecotoxicity measurements were carried out on a bacterium (Photobacterium phosphoreum) according to the Microtox test, AFNOR NF T90-320, and on an alga (SJceletonei-ia costatum) according to the ISO / DIS 10253 method. The toxicity according to Microtox is expressed in LC5 0 (lethal concentration in mg / 1 to destroy 50% of the population in 15 minutes); the toxicity according to ISO / DIS 10253 is expressed in CE5 0 (effective concentration in mg / 1 to inhibit the growth of 50% of the population in 72 hours).
Le tableau ci-dessous donne les toxicités Microtox et sur Skeletonema costatum des formules étudiées :The table below gives the Microtox toxicities and on Skeletonema costatum of the formulas studied:
Produit Ecotoxicité Ecotoxicité "Microtox" S. costatum CE50 (mg/1) CE (mg/1) acide mercaptoacetique 45 >300 (à 100%) acide mercaptopropionique 450 97 (à 100%)Product Ecotoxicity Ecotoxicity "Microtox" S. costatum EC50 (mg / 1) EC (mg / 1) mercaptoacetic acid 45> 300 (100%) mercaptopropionic acid 450 97 (100%)
Dipropionamide (100%) 127 672Dipropionamide (100%) 127,672
Formule n°16 1350 2289Formula n ° 16 1350 2289
Formule n°17 22000 980
Figure imgf000011_0001
Formula n ° 17 22000 980
Figure imgf000011_0001

Claims

10REVENDICATIONS 10 CLAIMS
1. Procédé pour limiter la corrosion carbonique de l'acier dans les milieux aqueux, caractérisé en ce que l'on utilise, à titre d'inhibiteur de corrosion non écotoxique, une composition aqueuse comportant comme matière active1. Method for limiting carbonic corrosion of steel in aqueous media, characterized in that an aqueous composition comprising as active material is used as a non-ecotoxic corrosion inhibitor
- au moins l'un des polyméthylène-polyaminodipropionamides correspondant à la formule :- at least one of the polymethylene polyaminodipropionamides corresponding to the formula:
H2NCO- (CH2) 2-NH- (CH2) -NH]- (CH2) 2-CONH2 dans laquelle m est un nombre entier pouvant prendre toute valeur de 1 à , qui représente le nombre de maillons polyméthylène-amino -(CH2)n-NH- , n pouvant avoir dans chaque maillon polyméthylène-amino une valeur entière de 2 à 6,H 2 NCO- (CH 2 ) 2 -NH- (CH 2 ) -NH] - (CH 2 ) 2 -CONH 2 in which m is an integer which can take any value from 1 to, which represents the number of polymethylene links -amino - (CH 2 ) n -NH-, n being able to have in each polymethylene-amino link an integer value from 2 to 6,
- au moins un mercaptoacide répondant à la formule générale- at least one mercaptoacid corresponding to the general formula
R2 R4 R 2 R 4
R-, -fc -C-AR-, -fc -C-A
1 Ll q | 1 L lq |
R3 R5 avec q = 0 à 3, R 3 R 5 with q = 0 to 3,
Ri-H ou SH,Ri-H or SH,
R2 et R3, ensemble ou indépendamment = C1-.4, CON(Rg) (R7) ,R 2 and R 3 , together or independently = C1-.4, CON (Rg) (R7),
COOR8,COOR 8 ,
R4 et R5, ensemble ou indépendamment = OH, NH2, ou SH quand Rx≠SH,R 4 and R5, together or independently = OH, NH 2 , or SH when Rx ≠ SH,
Rg et R7, ensemble ou indépendamment = H, C1-.4,Rg and R 7 , together or independently = H, C 1 -.4,
R8 = H, Ci.β,R 8 = H, Ci.β,
R2 à R5 pouvant être inclus dans un cycle aliphatique,R 2 to R5 can be included in an aliphatic cycle,
R3 et R5 pouvant être inclus dans un cycle aromatique lorsque q=l,R 3 and R5 can be included in an aromatic cycle when q = l,
A étant un groupe acide COOH, SO3H, OSO3H, PO3H ou OPO3H, le rapport pondéral entre le ou les composants thioacides et le ou les composants dipropionamides étant compris entre 0,3 et 2. 11A being an acid group COOH, SO3H, OSO 3 H, PO 3 H or OPO 3 H, the weight ratio between the thioacid component (s) and the dipropionamide component (s) being between 0.3 and 2. 11
2. Procédé selon la revendication 1, caractérisé en ce que le mercaptoacide est un acide mercaptocarboxylique2. Method according to claim 1, characterized in that the mercaptoacid is a mercaptocarboxylic acid
R2 R4 R 2 R 4
Rη - c-^l-C-COOH L ! q I R3 R5 R η - c- ^ lC-COOH L ! q IR 3 R 5
3. Procédé selon la revendication 1, caractérisé en ce que le mercaptoacide est l'acide mercaptoacetique.3. Method according to claim 1, characterized in that the mercaptoacid is mercaptoacetic acid.
4. Procédé selon la revendication 1, caractérisé en ce que le mercaptoacide est l'acide mercaptopropionique . 4. Method according to claim 1, characterized in that the mercaptoacid is mercaptopropionic acid.
5. Procédé selon l'une ou l'autre des revendications 1 à 4, caractérisé en ce que la composition inhibitrice est utilisée en traitement continu à raison de 3 à 100 ppm, exprimées en poids des matières actives, mercaptoacides + polyméthylène-polyaminodipropionamides, par rapport au poids du milieu corrosif.5. Method according to either of claims 1 to 4, characterized in that the inhibitor composition is used in continuous treatment at a rate of 3 to 100 ppm, expressed by weight of the active materials, mercaptoacids + polymethylene-polyaminodipropionamides, relative to the weight of the corrosive medium.
6. Procédé selon l'une ou l'autre des revendications 1 à 4, caractérisé en ce que la composition inhibitrice est utilisée en traitement séquence à raison de 1 % à 10 %, exprimés en poids des matières actives, mercaptoacides + polyméthylène-polyaminodipropionamides, par rapport au fluide porteur .6. Method according to either of claims 1 to 4, characterized in that the inhibitor composition is used in sequential treatment at a rate of 1% to 10%, expressed by weight of the active materials, mercaptoacids + polymethylene-polyaminodipropionamides , with respect to the carrier fluid.
7. Compositions inhibitrices pour limiter la corrosion carbonique de l'acier dans les milieux aqueux, constituées d'une solution aqueuse comportant - au moins l'un des polyméthylène-polyaminodipropionamides correspondant à la formule :7. Inhibiting compositions for limiting carbon dioxide corrosion of steel in aqueous media, consisting of an aqueous solution comprising - at least one of the polymethylene-polyaminodipropionamides corresponding to the formula:
H2NCO- (CH2) 2-NH- (CH2) —NH - (CH2) 2 ~CONH2 dans laq-uelle m est un nombre entier pouvant prendre toute valeur de 1 à 4 , qui représente le nombre de maillons polyméthylène-amino -(CH2)n-NH- , n pouvant avoir dans cha-que maillon polyméthylène-amino une valeur entière de 2 à 6, 12H 2 NCO- (CH 2 ) 2 -NH- (CH 2 ) —NH - (CH 2 ) 2 ~ CONH 2 in which m is an integer which can take any value from 1 to 4, which represents the number of polymethylene-amino links - (CH 2 ) n -NH-, n being able to have in each that polyethylene-amino link an integer value from 2 to 6, 12
• au moins un mercaptoacide répondant à la formule générale• at least one mercaptoacid corresponding to the general formula
R2 R4 R 2 R 4
R •ii--t+-C'- -C-A q ιR • ii - t + -C'- -CA q ι
R3 R,R 3 R,
avec q = 0 à 3,with q = 0 to 3,
R1=H ou SH,R 1 = H or SH,
R et R3, ensemble ou indépendamment = C1-. . CON(Rg) (R7) ,R and R 3 , together or independently = C 1 -. . CON (Rg) (R7),
COOR8, R4 et R5, ensemble ou indépendamment = OH, NH2, ou SH quandCOOR 8 , R4 and R5, together or independently = OH, NH 2 , or SH when
Ri≠SH,Ri ≠ SH,
Rg et R7, ensemble ou indépendamment = H, C^-^,Rg and R 7 , together or independently = H, C ^ - ^,
R8 = H, Ci.g,R 8 = H, Ci.g,
R2 à R5 pouvant être inclus dans un cycle aliphatique, R3 et R5 pouvant être inclus dans un cycle aromatique lorsque q=l,R 2 to R5 can be included in an aliphatic cycle, R3 and R5 can be included in an aromatic cycle when q = l,
A étant un groupe acide COOH, SO3H, OSO3H, PO3H ou OPO3H, le rapport pondéral entre le ou les composants thioacides et le ou les composants dipropionamides étant compris entre 0 , 3 et 2. la teneur pondérale en composants actifs, dipropionamides et thioacides étant comprise entre 10 et 75 % .A being an acid group COOH, SO 3 H, OSO 3 H, PO3H or OPO 3 H, the weight ratio between the thioacid component (s) and the dipropionamide component (s) being between 0, 3 and 2. the weight content of components active, dipropionamides and thioacids being between 10 and 75%.
8. Compositions selon la revendication 7, caractérisées en ce que le mercaptoacide est un acide mercaptocarboxylique8. Compositions according to claim 7, characterized in that the mercaptoacid is a mercaptocarboxylic acid
Ro R-ιRo R-ι
Rχ- C- -C-COOH qιRχ- C- -C-COOH qι
R3 R5 R 3 R 5
9. Compositions selon la revendication 7, caractérisées en ce que le mercaptoacide est l'acide mercaptoacetique.9. Compositions according to claim 7, characterized in that the mercaptoacid is mercaptoacetic acid.
10. Compositions selon la revendication 7, caractérisées en ce que le mercaptoacide est l'acide mercaptopropionique. 10. Compositions according to claim 7, characterized in that the mercaptoacid is mercaptopropionic acid.
PCT/FR1999/000163 1998-02-02 1999-01-28 Ecologically compatible carbon corrosion inhibitors of iron WO1999039025A1 (en)

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CN100385041C (en) * 2002-01-29 2008-04-30 兰爱克谢斯德国有限责任公司 Corrosion inhibitor for protecting metal material in strong base medium
WO2018136472A2 (en) 2017-01-17 2018-07-26 Baker Hughes, A Ge Company, Llc Synergistic corrosion inhibitors

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WO2018136472A2 (en) 2017-01-17 2018-07-26 Baker Hughes, A Ge Company, Llc Synergistic corrosion inhibitors

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