EP0931854A1 - Corrosion inhibiting of stainless steel in organic sulphonic acid - Google Patents

Corrosion inhibiting of stainless steel in organic sulphonic acid Download PDF

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Publication number
EP0931854A1
EP0931854A1 EP98403065A EP98403065A EP0931854A1 EP 0931854 A1 EP0931854 A1 EP 0931854A1 EP 98403065 A EP98403065 A EP 98403065A EP 98403065 A EP98403065 A EP 98403065A EP 0931854 A1 EP0931854 A1 EP 0931854A1
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Prior art keywords
cerium
mole
acid
salt
stainless steel
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German (de)
French (fr)
Inventor
Jean Goudiakas
Guy Rousseau
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Arkema France SA
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Elf Atochem SA
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/04—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
    • C—CHEMISTRY; METALLURGY
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/40—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing molybdates, tungstates or vanadates
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
    • C23C22/50—Treatment of iron or alloys based thereon
    • 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
    • C23F11/18—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 inorganic inhibitors

Definitions

  • the present invention relates to the field of stainless steels and that organosulfonic acids. It has more particularly the object of protection stainless steels against corrosion by organosulfonic acids such as methanesulfonic acid.
  • Methanesulfonic acid is a strong acid which has found many applications, in particular in catalysis and in surface treatment (electroplating, pickling, descaling, ).
  • AMS aqueous solutions attack stainless steels; corrosion rates depend on the AMS concentration, the temperature and the nature of the stainless steel.
  • type 304L stainless steel is corrodable at concentrations of AMS greater than 10 -2 mole / liter. It is obvious that this drastically limits the fields of use of AMS.
  • the subject of the invention is therefore a process for protecting stainless steels against corrosion by an organosulfonic acid, characterized in that one adds at least one selected oxidant to the aqueous organosulfonic acid solution among the salts or oxides of cerium (IV), iron (III), molybdenum (VI) or vanadium (V), nitrites and persulfates.
  • the subject of the invention is also an aqueous solution of organosulfonic acid containing at least one oxidant chosen from the salts or oxides of cerium (IV), iron (III), molybdenum (VI) or vanadium (V), nitrites and persulfates in an amount sufficient for its spontaneous potential, measured by means of a stainless steel electrode, lies in the passivity zone determined in the same conditions in the absence of the oxidant.
  • oxidant chosen from the salts or oxides of cerium (IV), iron (III), molybdenum (VI) or vanadium (V), nitrites and persulfates in an amount sufficient for its spontaneous potential, measured by means of a stainless steel electrode, lies in the passivity zone determined in the same conditions in the absence of the oxidant.
  • Stainless steels are passivable materials. Physically, the passivity is due to the formation of a layer of oxides on the surface of the metal. The passivity is ultimately imparted to the alloy by the development of a layer adherent and relatively thin, but of very low ionic permeability. The transfer of cations from metal to solution can be considered very slow and, in some cases, practically negligible. In fact, the phenomenon of passivity must be considered as a state of dynamic equilibrium.
  • organosulfonic acid or in the solution aqueous organosulfonic acid, the nature of the oxidant chosen is not critical and it is therefore possible to use any soluble salt or oxide of cerium (IV), iron (III), molybdenum (VI) or vanadium (V), as well as any soluble nitrite or persulfate.
  • iron (III) sulfate ferric chloride, ferric nitrate, ferric perchlorate, ferric oxide, sodium molybdate, ammonium molybdate tetrahydrate, molybdenum oxide, sodium metavanadate, oxytrichloride vanadium, vanadium pentoxide, sodium persulfate and ammonium persulfate.
  • the amount of oxidant according to the invention to be used can vary within wide limits; it depends, among other things, on the nature of the oxidant and the concentration of organosulfonic acid.
  • concentration of Ce 4+ ions is generally between 1.10 -5 and 1.10 -1 mole / liter; it is preferably between 1.10 -4 and 5.10 -2 mole / liter.
  • the amount used is generally between 1.10 -4 and 1 mole / liter; it is preferably between 0.001 and 0.5 mole / liter.
  • a particularly advantageous embodiment of the process according to the invention consists in combining a molybdenum (VI) salt, preferably sodium molybdate, and a cerium (IV) salt, preferably a double ammonium salt and of cerium (IV).
  • the amount of each salt to be used can vary within wide limits, but it is preferably between 1.10 -3 and 2.10 -2 mole / liter and, more particularly, between 5.10 -3 and 1.10 -2 mole / liter.
  • the invention relates more particularly to methanesulfonic acid (AMS).
  • AMS methanesulfonic acid
  • the protection method according to the invention can nevertheless be applied to other alkanesulfonic acids, for example ethanesulfonic acid, or to acids aromatic sulfonics such as p-toluenesulfonic acid (APTS).
  • alkanesulfonic acids for example ethanesulfonic acid
  • APTS p-toluenesulfonic acid
  • the test involves immersing an electrode made from the material studied in the solution to be tested and to verify that its spontaneous potential, in regime stabilized, is effectively in the area of passivation. Before the test, we polarizes in the cathode domain for 30 seconds.
  • the electrolysis cell consists of a container that can contain 80 ml of the solution to be tested and allows mounting of three electrodes: one electrode reference (Ag / Ag Cl of the Thermag-Tacussel type), an auxiliary electrode (platinum) and a working electrode (studied stainless steel).
  • the coupons are degreased with acetone, pickled in a 15% aqueous solution of nitric acid and 4.2% of sodium fluoride, rinsed with demineralized water, then with acetone, dried with de-oiled compressed air and weighed.
  • the coupons After immersion for 8 or 30 days in the AMS solution to be tested, the coupons are washed with demineralized water and then with acetone, weighed, cleared possible deposits (corrosion products) by mechanical cleaning and weighed at new.
  • the loss of mass expressed in g / m 2 .j, makes it possible to calculate the corrosion rate expressed in mm / year.
  • electrochemical tests were carried out at 45 and 90 ° C for an AMS concentration of 2.08 M and for two grades of steel stainless (AISI 304L and 316L) previously subjected to a heat treatment of hyper quenching according to standard NF A35-574.
  • Corrosive baths consisted of AMS 2.08 moles / liter aqueous solutions containing varying amounts of sodium nitrite or double nitrate of ammonium and cerium (IV).
  • the spontaneous potential is always located between the passivation potentials and transpassivation. The risks of generalized corrosion are therefore negligible.
  • aqueous solutions S 1 , S 2 and S 3 having the following mass composition were prepared from a 70% aqueous solution of AMS and a 65% aqueous solution of APTS.
  • SOLUTION CONTENT (% by mass) in: AMS APTS Water S 1 24.5 9.75 65.75 S 2 49 19.5 31.5 S 3 0.5 0.2 99.3
  • Static corrosion tests were carried out at 45 ° C (duration: 8 days) in more or less diluted aqueous solutions of AMS.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
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Abstract

Stainless steel is protected against organosulfonic acid corrosion by adding a specified oxidizing agent to the acid. Stainless steel is protected against corrosion by an organosulfonic acid by adding an oxidizing agent selected from the salts or oxides of cerium (IV), iron (III), molybdenum (VI) or vanadium (V), nitrites and persulfates to an aqueous solution of the acid. An Independent claim is also included for an aqueous organosulfonic acid solution containing the oxidizing agent described above in amount such that its spontaneous potential, measured by a stainless steel electrode, is located in the passivity zone determined under the same conditions but in the absence of the oxidizing agent. Preferred Features: The oxidizing agent addition comprises 1 x 10<-4> to 1 (especially 0.001-0.5) mole/l alkali metal (especially sodium) nitrite; 1 x 10<-5> to 1 x 10<-1> (especially 1 x 10<-4> to 5 x 10<-2>) mole/l Ce<4+> ions; or 1 x 10<-3> to 2 x 10<-2> (especially 5 x 10<-3> to 1 x 10<-2>) mole/l each of a molybdenum (VI) salt and a cerium (IV) salt.

Description

La présente invention concerne le domaine des aciers inoxydables et celui des acides organosulfoniques. Elle a plus particulièrement pour objet la protection des aciers inoxydables contre la corrosion par les acides organosulfoniques tels que l'acide méthanesulfonique.The present invention relates to the field of stainless steels and that organosulfonic acids. It has more particularly the object of protection stainless steels against corrosion by organosulfonic acids such as methanesulfonic acid.

L'acide méthanesulfonique (AMS) est un acide fort qui a trouvé de nombreuses applications, notamment en catalyse et en traitement de surfaces (galvanoplastie, décapage, détartrage, ...). Cependant, les solutions aqueuse d'AMS attaquent les aciers inoxydables; les vitesses de corrosion dépendent à la fois de la concentration en AMS, de la température et de la nature de l'acier inoxydable. Ainsi, à température ambiante, l'acier inoxydable du type 304L est corrodable à des concentrations d'AMS supérieures à 10-2 mole/litre. Il est évident que cela limite de manière drastique les domaines d'utilisation de l'AMS.Methanesulfonic acid (AMS) is a strong acid which has found many applications, in particular in catalysis and in surface treatment (electroplating, pickling, descaling, ...). However, AMS aqueous solutions attack stainless steels; corrosion rates depend on the AMS concentration, the temperature and the nature of the stainless steel. Thus, at room temperature, type 304L stainless steel is corrodable at concentrations of AMS greater than 10 -2 mole / liter. It is obvious that this drastically limits the fields of use of AMS.

Pour protéger les aciers inoxydables contre la corrosion par des acides sulfoniques (en particulier l'acide p-toluènesulfonique et l'acide polystyrènesulfonique), il a été proposé dans la demande de brevet JP 07-278854 d'ajouter à ces acides un sel de cuivre. Ce document vise plus particulièrement la protection des appareils en acier inoxydable (types 304 et 316) utilisés dans les ateliers de synthèse d'alcools à partir d'oléfines et d'eau en présence d'un acide organosulfonique comme catalyseur. Le domaine de température exemplifié dans ce document va de la température ambiante jusqu'à environ 100°C.To protect stainless steels from corrosion by acids sulfonic (in particular p-toluenesulfonic acid and polystyrenesulfonic acid), it was proposed in patent application JP 07-278854 to add to these acids a copper salt. This document aims more particularly at the protection of stainless steel appliances (types 304 and 316) used in workshops synthesis of alcohols from olefins and water in the presence of an organosulfonic acid as a catalyst. The temperature range exemplified in this document will from room temperature to around 100 ° C.

Dans l'article intitulé "Corrosion of stainless steel during acetate production" paru en juillet 1996 dans la revue Corrosion Engineering vol.2, n°7, page 558, J.S. Qi et J.C. Lester indiquent que l'utilisation de sulfate de cuivre lors de l'estérification en présence d'acide sulfurique ou d'acide p-toluénesulfonique permet de réduire considérablement la corrosion des aciers inox 304L et 316L.In the article titled "Corrosion of stainless steel during acetate production" published in July 1996 in the journal Corrosion Engineering vol.2, n ° 7, page 558, J.S. Qi and J.C. Lester indicate that the use of copper sulphate during esterification in the presence of sulfuric acid or p-toluenesulfonic acid reduces considerable corrosion of 304L and 316L stainless steels.

Cependant, les tests statiques effectués sur des compositions d'AMS et de sels de cuivre (II) à des températures comprises entre 100 et 150°C montrent qu'à la surface des matériaux testés (AISI 304L et 316L) il se forme une fine couche de cuivre métallique peu adhérente. Lors de la mise en oeuvre industrielle de cette méthode, il a en effet été constaté une sédimentation, en fond de réacteur, de particules de cuivre métal susceptibles d'endommager gravement les pompes de recyclage ou de nuire à la qualité du produit fabriqué. Une étape supplémentaire de filtration est alors nécessaire pour éliminer ces particules de cuivre provenant de la pellicule déposée sur les parois du réacteur. En fait, lors de changements de conditions opératoires (par exemple, température, pression, vitesse d'agitation), cette pellicule protectrice se détache très facilement. However, static tests performed on AMS and copper (II) salts at temperatures between 100 and 150 ° C show that at the surface of the tested materials (AISI 304L and 316L) a thin layer of poorly adherent metallic copper. During the industrial implementation of this method, it has indeed been found a sedimentation, at the bottom of the reactor, of particles copper metal can seriously damage recycling pumps or adversely affect the quality of the product produced. An additional step of filtration is then necessary to remove these copper particles from the film deposited on the walls of the reactor. In fact, when conditions change procedures (e.g. temperature, pressure, agitation speed), this protective film comes off very easily.

Il a maintenant été trouvé que l'on peut efficacement protéger, dans une large gamme de température, les aciers inoxydables contre la corrosion par les acides organosulfoniques et, en particulier, par l'AMS en ajoutant au milieu un oxydant choisi parmi les sels ou oxydes de cérium (IV), de fer (III), de molybdène (VI) ou de vanadium (V), les nitrites et les persulfates.It has now been found that one can effectively protect, in a wide temperature range, stainless steels against acid corrosion organosulfonic and, in particular, by AMS by adding an oxidant to the medium chosen from the salts or oxides of cerium (IV), iron (III), molybdenum (VI) or vanadium (V), nitrites and persulfates.

L'invention a donc pour objet un procédé pour protéger les aciers inoxydables contre la corrosion par un acide organosulfonique, caractérisé en ce que l'on ajoute à la solution aqueuse d'acide organosulfonique au moins un oxydant choisi parmi les sels ou oxydes de cérium (IV), de fer (III), de molybdène (VI) ou de vanadium (V), les nitrites et les persulfates.The subject of the invention is therefore a process for protecting stainless steels against corrosion by an organosulfonic acid, characterized in that one adds at least one selected oxidant to the aqueous organosulfonic acid solution among the salts or oxides of cerium (IV), iron (III), molybdenum (VI) or vanadium (V), nitrites and persulfates.

L'invention a également pour objet une solution aqueuse d'acide organosulfonique contenant au moins un oxydant choisi parmi les sels ou oxydes de cérium (IV), de fer (III), de molybdène (VI) ou de vanadium (V), les nitrites et les persulfates en une quantité suffisante pour que son potentiel spontané, mesuré au moyen d'une électrode en acier inoxydable, se situe dans la zone de passivité déterminée dans les mêmes conditions en l'absence de l'oxydant.The subject of the invention is also an aqueous solution of organosulfonic acid containing at least one oxidant chosen from the salts or oxides of cerium (IV), iron (III), molybdenum (VI) or vanadium (V), nitrites and persulfates in an amount sufficient for its spontaneous potential, measured by means of a stainless steel electrode, lies in the passivity zone determined in the same conditions in the absence of the oxidant.

Les aciers inoxydables sont des matériaux passivables. Physiquement, la passivité est due à la formation d'une couche d'oxydes à la surface du métal. La passivité est finalement conférée à l'alliage par le développement d'une couche adhérente et relativement peu épaisse, mais de très faible perméabilité ionique. Le transfert des cations du métal vers la solution peut être considéré comme très ralenti et, dans certains cas, pratiquement négligeable. En fait, le phénomène de passivité doit être considéré comme un état d'équilibre dynamique.Stainless steels are passivable materials. Physically, the passivity is due to the formation of a layer of oxides on the surface of the metal. The passivity is ultimately imparted to the alloy by the development of a layer adherent and relatively thin, but of very low ionic permeability. The transfer of cations from metal to solution can be considered very slow and, in some cases, practically negligible. In fact, the phenomenon of passivity must be considered as a state of dynamic equilibrium.

La vitesse de dissolution (v) d'un acier inoxydable immergé dans un milieu tel qu'une solution aqueuse d'AMS 1M dépend du potentiel électrochimique imposé E. La courbe v = f(E) présente une allure typique qui, comme montré sur la figure unique annexée, comprend essentiellement trois parties, à savoir :

  • une zone "d'activité" 1 correspondant à la dissolution anodique du métal (oxydation),
  • une zone de "passivité" 2 située entre un potentiel de passivation (Ep) et un potentiel de transpassivation (Etp),
  • une zone de "transpassivité" 3 où le métal redevient actif par oxydation du film passif en une substance soluble (dissolution du Cr2O3 en CrO4 2-).
The dissolution rate (v) of a stainless steel immersed in a medium such as an aqueous solution of AMS 1M depends on the electrochemical potential imposed E. The curve v = f (E) has a typical appearance which, as shown in the single appended figure, essentially comprises three parts, namely:
  • an "activity" zone 1 corresponding to the anodic dissolution of the metal (oxidation),
  • a "passivity" zone 2 situated between a passivation potential (Ep) and a transpassivation potential (Etp),
  • a "transpassivity" zone 3 where the metal becomes active again by oxidation of the passive film into a soluble substance (dissolution of Cr 2 O 3 into CrO 4 2- ).

Au potentiel de passivité Ep, la vitesse de corrosion est tombée brusquement à une valeur très faible. Dans la zone 2, la vitesse de dissolution très faible correspond alors à un domaine de résistance à la corrosion. La mesure du potentiel spontané et sa comparaison avec Ep et Etp permet de déterminer instantanément si l'acier inoxydable se corrode ou non. At the passivity potential Ep, the corrosion rate dropped suddenly at a very low value. In zone 2, the very low dissolution rate corresponds then to an area of corrosion resistance. Measuring potential spontaneous and its comparison with Ep and Etp makes it possible to instantly determine whether stainless steel corrodes or not.

Pourvu qu'il soit soluble dans l'acide organosulfonique ou dans la solution aqueuse d'acide organosulfonique, la nature de l'oxydant choisi n'est pas critique et on peut donc utiliser tout sel ou oxyde soluble de cérium (IV), de fer (III), de molybdène (VI) ou de vanadium (V), ainsi que tout nitrite ou persulfate soluble.Provided it is soluble in organosulfonic acid or in the solution aqueous organosulfonic acid, the nature of the oxidant chosen is not critical and it is therefore possible to use any soluble salt or oxide of cerium (IV), iron (III), molybdenum (VI) or vanadium (V), as well as any soluble nitrite or persulfate.

Sont plus particulièrement préférés :

  • les nitrites alcalins, d'ammonium ou de cuivre et, plus spécialement, le nitrite de sodium,
  • les sels doubles d'ammonium et de cérium (IV) tels que le nitrate ou le sulfate d'ammonium et de cérium.
The following are more particularly preferred:
  • alkali, ammonium or copper nitrites and, more particularly, sodium nitrite,
  • double ammonium and cerium (IV) salts such as ammonium and cerium nitrate or sulphate.

Comme exemples non limitatifs d'autres oxydants selon l'invention, on peut également mentionner le sulfate de fer (III), le chlorure ferrique, le nitrate ferrique, le perchlorate ferrique, l'oxyde ferrique, le molybdate de sodium, le molybdate d'ammonium tétrahydraté, l'oxyde de molybdène, le métavanadate de sodium, l'oxytrichlorure de vanadium, le pentoxyde de vanadium, le persulfate de sodium et le persulfate d'ammonium.As nonlimiting examples of other oxidants according to the invention, it is possible to also mention iron (III) sulfate, ferric chloride, ferric nitrate, ferric perchlorate, ferric oxide, sodium molybdate, ammonium molybdate tetrahydrate, molybdenum oxide, sodium metavanadate, oxytrichloride vanadium, vanadium pentoxide, sodium persulfate and ammonium persulfate.

La quantité d'oxydant selon l'invention à utiliser peut varier dans de larges limites; elle dépend, entre autres, de la nature de l'oxydant et de la concentration en acide organosulfonique. Lorsqu'on utilise un sel cérique, la concentration en ions Ce4+ est généralement comprise entre 1.10-5 et 1.10-1 mole/litre; elle est, de préférence, comprise entre 1.10-4 et 5.10-2 mole/litre.The amount of oxidant according to the invention to be used can vary within wide limits; it depends, among other things, on the nature of the oxidant and the concentration of organosulfonic acid. When using a ceric salt, the concentration of Ce 4+ ions is generally between 1.10 -5 and 1.10 -1 mole / liter; it is preferably between 1.10 -4 and 5.10 -2 mole / liter.

Lorsqu'on utilise un nitrite ou un autre oxydant, la quantité utilisée est généralement comprise entre 1.10-4 et 1 mole/litre ; elle est de préférence comprise entre 0,001 et 0,5 mole/litre.When using a nitrite or other oxidant, the amount used is generally between 1.10 -4 and 1 mole / liter; it is preferably between 0.001 and 0.5 mole / liter.

Un mode particulièrement avantageux de mise en oeuvre du procédé selon l'invention consiste à associer un sel de molybdène (VI), de préférence le molybdate de sodium, et un sel de cérium (IV), de préférence un sel double d'ammonium et de cérium (IV). La quantité de chaque sel à utiliser peut varier dans de larges limites, mais elle est de préférence comprise entre 1.10-3 et 2.10-2 mole/litre et, plus particulièrement, entre 5.10-3 et 1.10-2 mole/litre.A particularly advantageous embodiment of the process according to the invention consists in combining a molybdenum (VI) salt, preferably sodium molybdate, and a cerium (IV) salt, preferably a double ammonium salt and of cerium (IV). The amount of each salt to be used can vary within wide limits, but it is preferably between 1.10 -3 and 2.10 -2 mole / liter and, more particularly, between 5.10 -3 and 1.10 -2 mole / liter.

Bien que le procédé selon l'invention vise plus spécialement la protection des aciers inoxydables courants (types AISI 304L et 316L), il peut s'appliquer généralement à tout acier inoxydable tel que défini dans la norme NF EN 10088-1.Although the process according to the invention more specifically aims at protection common stainless steels (types AISI 304L and 316L), it can generally be applied all stainless steel as defined in standard NF EN 10088-1.

L'invention concerne plus particulièrement l'acide méthanesulfonique (AMS). Le procédé de protection selon l'invention peut néanmoins s'appliquer à d'autres acides alcanesulfoniques, par exemple l'acide éthanesulfonique, ou à des acides sulfoniques aromatiques tels que l'acide p-toluénesulfonique (APTS).The invention relates more particularly to methanesulfonic acid (AMS). The protection method according to the invention can nevertheless be applied to other alkanesulfonic acids, for example ethanesulfonic acid, or to acids aromatic sulfonics such as p-toluenesulfonic acid (APTS).

Dans les exemples suivants qui illustrent l'invention sans la limiter, les essais électrochimiques et statiques ont été réalisés en opérant comme suit. In the following examples which illustrate the invention without limiting it, the tests electrochemical and static were carried out by operating as follows.

1. Essais électrochimiques 1. Electrochemical tests

L'essai consiste à plonger une électrode fabriquée à partir du matériau étudié dans la solution à tester et à vérifier que son potentiel spontané, en régime stabilisé, se trouve effectivement dans le domaine de la passivation. Avant le test, on réalise une polarisation dans le domaine cathodique pendant 30 secondes.The test involves immersing an electrode made from the material studied in the solution to be tested and to verify that its spontaneous potential, in regime stabilized, is effectively in the area of passivation. Before the test, we polarizes in the cathode domain for 30 seconds.

La cellule d'électrolyse est constituée d'un récipient pouvant contenir 80 ml de la solution à tester et permet un montage de trois électrodes : une électrode de référence (Ag/Ag Cl du type Thermag-Tacussel), une électrode auxiliaire (platine) et une électrode de travail (acier inoxydable étudié).The electrolysis cell consists of a container that can contain 80 ml of the solution to be tested and allows mounting of three electrodes: one electrode reference (Ag / Ag Cl of the Thermag-Tacussel type), an auxiliary electrode (platinum) and a working electrode (studied stainless steel).

2. Essais statiques 2. Static tests

Ces essais permettent, d'une part, de vérifier la passivité des matériaux et, d'autre part, de calculer la vitesse de corrosion.These tests allow, on the one hand, to verify the passivity of the materials and, on the other hand, to calculate the corrosion rate.

L'étude de la corrosion par perte de masse est réalisée à partir de plaquettes métalliques découpées à l'aide d'une tronçonneuse à disque lubrifié. La surface de ces coupons de dimensions approximatives : 25x50x2 mm est calculée avec précision. Ces coupons métalliques sont percés d'un trou de 6,5 mm de diamètre permettant de les fixer sur un porte-échantillon en Téflon.The study of corrosion by loss of mass is carried out from metal inserts cut using a chainsaw with lubricated disc. The area of these coupons of approximate dimensions: 25x50x2 mm is calculated precisely. These metal coupons are drilled with a 6.5 mm diameter hole allowing to fix them on a Teflon sample holder.

Avant leur immersion dans la solution d'AMS à tester, les coupons sont dégraissés à l'acétone, décapés dans une solution aqueuse à 15 % d'acide nitrique et 4,2 % de fluorure de sodium, rincés à l'eau déminéralisée, puis à l'acétone, séchés à l'air comprimé déshuilé et pesés.Before their immersion in the AMS solution to be tested, the coupons are degreased with acetone, pickled in a 15% aqueous solution of nitric acid and 4.2% of sodium fluoride, rinsed with demineralized water, then with acetone, dried with de-oiled compressed air and weighed.

Après immersion pendant 8 ou 30 jours dans la solution d'AMS à tester, les coupons sont lavés à l'eau déminéralisée puis à l'acétone, pesés, débarrassés des éventuels dépôts (produits de corrosion) par nettoyage mécanique et pesés à nouveau.After immersion for 8 or 30 days in the AMS solution to be tested, the coupons are washed with demineralized water and then with acetone, weighed, cleared possible deposits (corrosion products) by mechanical cleaning and weighed at new.

La perte de masse, exprimée en g/m2.j, permet de calculer la vitesse de corrosion exprimée en mm/an.The loss of mass, expressed in g / m 2 .j, makes it possible to calculate the corrosion rate expressed in mm / year.

EXEMPLE 1EXAMPLE 1

L'outil électrochimique étant particulièrement bien adapté à la vérification des états passifs des aciers inoxydables, des tests électrochimiques ont été effectués à 45 et 90°C pour une concentration en AMS de 2,08 M et pour deux nuances d'acier inoxydable (AISI 304L et 316L) préalablement soumises à un traitement thermique d'hypertrempe selon la norme NF A35-574. Les bains corrosifs étaient constitués de solutions aqueuses d'AMS à 2,08 moles/litre contenant des quantités variables de nitrite de sodium ou de nitrate double d'ammonium et de cérium (IV).The electrochemical tool being particularly well suited to the verification of passive states of stainless steels, electrochemical tests were carried out at 45 and 90 ° C for an AMS concentration of 2.08 M and for two grades of steel stainless (AISI 304L and 316L) previously subjected to a heat treatment of hyper quenching according to standard NF A35-574. Corrosive baths consisted of AMS 2.08 moles / liter aqueous solutions containing varying amounts of sodium nitrite or double nitrate of ammonium and cerium (IV).

Les résultats obtenus sont rassemblés dans les tableaux I et II suivants qui indiquent en mV les potentiels (E) de passivation, spontané et de transpassivation.. Essais électrochimiques dans AMS 2,08 M pour l'acier inox 316L Température 45°C 90°C 45°C 90°C Additif et sa concentration (mole/litre) NaNO2 (NH4)2 Ce(NO3)6 0,05 0,08 0,005 0,01 E passivation -100 255 25 0 E spontané 540 615 1000 420 E transpassivation 1100 690 1100 750 Essais électrochimiques dans AMS 2,08 M pour l'acier inox 304L Température 45°C 90°C 45°C 90°C Additif et sa concentration (mole/litre) NaNO2 (NH4)2 Ce(NO3)6 0,05 0,3 0,01 0,0175 E passivation -100 -45 0 20 E spontané 600 400 1000 470 E transpassivation 1100 950 1150 950 The results obtained are collated in the following Tables I and II which indicate in mV the potentials (E) of passivation, spontaneous and transpassivation. Electrochemical tests in AMS 2.08 M for 316L stainless steel Temperature 45 ° C 90 ° C 45 ° C 90 ° C Additive and its concentration (mole / liter) NaNO 2 (NH 4 ) 2 Ce (NO 3 ) 6 0.05 0.08 0.005 0.01 E passivation -100 255 25 0 E spontaneous 540 615 1000 420 E transpassivation 1100 690 1100 750 Electrochemical tests in AMS 2.08 M for 304L stainless steel Temperature 45 ° C 90 ° C 45 ° C 90 ° C Additive and its concentration (mole / liter) NaNO 2 (NH 4 ) 2 Ce (NO 3 ) 6 0.05 0.3 0.01 0.0175 E passivation -100 -45 0 20 E spontaneous 600 400 1000 470 E transpassivation 1100 950 1150 950

Le potentiel spontané est toujours situé entre les potentiels de passivation et de transpassivation. Les risques de corrosion généralisée sont donc négligeables.The spontaneous potential is always located between the passivation potentials and transpassivation. The risks of generalized corrosion are therefore negligible.

EXEMPLE 2EXAMPLE 2

Pour étendre les résultats de l'exemple 1, des essais statiques ont été effectués à 150°C. Les résultats sont regroupés dans le tableau III suivant. Essais statiques à 150°C dans AMS 2,08 M Acier inoxydable Additif et sa concentration (mole/litre) Perte de masse (g/m2.j) Vitesse de corrosion (mm/an) 316 L Néant - > 500 > 23 NaNO2 0,16 0,29 0,013 (NH4)2 Ce(NO3)6 0,01 3,15 0,14 304 L Néant - > 500 > 23 NaNO2 0,3 0,27 0,013 (NH4)2 Ce(NO3)6 0,0175 0,49 0,022 To extend the results of Example 1, static tests were carried out at 150 ° C. The results are collated in Table III below. Static tests at 150 ° C in AMS 2.08 M Stainless steel Additive and its concentration (mole / liter) Weight loss (g / m 2 .j) Corrosion rate (mm / year) 316 L None - > 500 > 23 NaNO 2 0.16 0.29 0.013 (NH 4 ) 2 Ce (NO 3 ) 6 0.01 3.15 0.14 304 L None - > 500 > 23 NaNO 2 0.3 0.27 0.013 (NH 4 ) 2 Ce (NO 3 ) 6 0.0175 0.49 0.022

EXEMPLE 3EXAMPLE 3

En opérant comme à l'exemple 1, on a étudié l'effet protecteur d'autres espèces pour l'acier inoxydable 316L. Ces essais et leurs résultats sont rassemblés dans le tableau IV suivant. Additif et concentration (mole/litre) Fe2(SO4)3 0,1 Na2MoO4 0,15 NaVO3 0,1 (NH4)2S2O8 0,1 Température (°C) 45 90 90 90 E passivation 0 373 0 331 E spontané 678 400 905 610 E transpassivation 1000 985 990 995 By operating as in Example 1, the protective effect of other species was studied for 316L stainless steel. These tests and their results are collated in the following Table IV. Additive and concentration (mole / liter) Fe 2 (SO 4 ) 3 0.1 Na 2 MoO 4 0.15 NaVO 3 0.1 (NH 4 ) 2 S 2 O 8 0.1 Temperature (° C) 45 90 90 90 E passivation 0 373 0 331 E spontaneous 678 400 905 610 E transpassivation 1000 985 990 995

EXEMPLE 4EXAMPLE 4

A partir d'une solution aqueuse à 70 % d'AMS et d'une solution aqueuse à 65 % d'APTS, on a préparé trois solutions aqueuses S1, S2 et S3 ayant la composition massique suivante : SOLUTION TENEUR (% massique) en : AMS APTS Eau S1 24,5 9,75 65,75 S2 49 19,5 31,5 S3 0,5 0,2 99,3 Three aqueous solutions S 1 , S 2 and S 3 having the following mass composition were prepared from a 70% aqueous solution of AMS and a 65% aqueous solution of APTS. SOLUTION CONTENT (% by mass) in: AMS APTS Water S 1 24.5 9.75 65.75 S 2 49 19.5 31.5 S 3 0.5 0.2 99.3

Deux oxydants :

  • Ox. 1 = nitrate double d'ammonium et de cérium (IV)
  • Ox. 2 = molybdate de sodium
ont été conjointement utilisés en proportions variables (5 à 10 millimoles/litres) pour passiver à différentes températures (45, 90 et 150°C) les aciers inoxydables 304L et 316L dans les solutions S1, S2 et S3.Two oxidants:
  • Ox. 1 = double ammonium and cerium (IV) nitrate
  • Ox. 2 = sodium molybdate
were jointly used in variable proportions (5 to 10 millimoles / liters) to passivate at different temperatures (45, 90 and 150 ° C) stainless steels 304L and 316L in solutions S 1 , S 2 and S 3 .

En opérant comme dans les exemples précédents, on a mesuré les potentiels de passivation, le potentiel spontané et le potentiel de transpassivation. Les résultats obtenus sont résumés dans les tableaux V et VI suivants ; ils montrent que le potentiel spontané est toujours situé entre les potentiels de passivation et de transpassivation. Les risques de corrosion généralisée sont donc négligeables. Acier Inox 304L Temp. (°C) Solution Teneur (mmol/l) Potentiels (mV) de : Ox.1 Ox.2 passivation spontané transpassivation 45 S1 10 5 -50 200 1020 " " 5 10 -50 220 1020 " S2 5 5 300 470 1100 " S3 5 5 0 900 1400 90 S1 5 5 -470 -50 1020 " " 10 10 300 380 1020 " S3 10 5 -100 848 900 " " 5 10 0 300 800 " S2 10 5 500 860 1100 " " 5 10 300 760 1120 150 S1 10 5 80 185 1020 " " 5 10 80 325 1020 " S3 5 5 80 740 1020 Acier Inox 316L Temp. (°C) Solution Teneur (mmol/l) Potentiels (mV) de : Ox.1 Ox.2 passivation spontané transpassivation 45 S1 10 5 -60 720 1100 " " 5 10 -80 450 1020 " S2 5 5 300 410 1100 " S3 5 5 100 325 1200 90 S1 5 5 80 515 1020 " " 10 10 300 494 1020 " S2 10 5 100 500 1200 " " 5 10 60 710 1200 " S3 10 5 -100 750 1080 " " 5 10 80 130 1020 By operating as in the previous examples, the passivation potentials, the spontaneous potential and the transpassivation potential were measured. The results obtained are summarized in Tables V and VI below; they show that the spontaneous potential is always located between the passivation and transpassivation potentials. The risks of generalized corrosion are therefore negligible. 304L stainless steel Temp. (° C) Solution Content (mmol / l) Potentials (mV) of: Ox.1 Ox.2 passivation spontaneous transpassivation 45 S 1 10 5 -50 200 1020 " " 5 10 -50 220 1020 " S 2 5 5 300 470 1100 " S 3 5 5 0 900 1400 90 S 1 5 5 -470 -50 1020 " " 10 10 300 380 1020 " S 3 10 5 -100 848 900 " " 5 10 0 300 800 " S 2 10 5 500 860 1100 " " 5 10 300 760 1120 150 S 1 10 5 80 185 1020 " " 5 10 80 325 1020 " S 3 5 5 80 740 1020 316L stainless steel Temp. (° C) Solution Content (mmol / l) Potentials (mV) of: Ox.1 Ox.2 passivation spontaneous transpassivation 45 S 1 10 5 -60 720 1100 " " 5 10 -80 450 1020 " S 2 5 5 300 410 1100 " S 3 5 5 100 325 1200 90 S 1 5 5 80 515 1020 " " 10 10 300 494 1020 " S 2 10 5 100 500 1200 " " 5 10 60 710 1200 " S 3 10 5 -100 750 1080 " " 5 10 80 130 1020

EXEMPLE 5EXAMPLE 5

On a effectué des essais statiques de corrosion à 45°C (durée : 8 jours) dans des solutions aqueuses d'AMS plus ou moins diluées.Static corrosion tests were carried out at 45 ° C (duration: 8 days) in more or less diluted aqueous solutions of AMS.

Ces solutions ont été préparées par addition d'eau à une solution initiale à 70 % en poids d'AMS contenant 5 mmoles/litre de nitrate double d'ammonium et de cérium (IV) et 5 mmoles/litre de molybdate de sodium.These solutions were prepared by adding water to an initial solution at 70% by weight of AMS containing 5 mmol / liter of double ammonium nitrate and cerium (IV) and 5 mmol / liter of sodium molybdate.

A titre comparatif, des essais statiques ont été effectuées en parallèle sur des solutions aqueuses d'AMS non additivées.For comparison, static tests were carried out in parallel on non-additive AMS aqueous solutions.

Dans les tableaux VII et VIII suivants qui résument les résultats obtenus, le chiffre de la colonne "dilution" indique la proportion (% en volume) d'AMS 70 % dans la solution aqueuse testée. Acier Inox 304L DILUTION VITESSE DE CORROSION (µm/an) AMS non additivé AMS additivé 1 < 5 < 5 5 465 <5 10 331 <5 25 541 <5 50 398 <5 100 - 45 Acier Inox 316L DILUTION VITESSE DE CORROSION (µm/an) AMS non additivé AMS additivé 1 < 5 < 5 5 75 <5 10 157 <5 25 190 <5 50 160 <5 100 - 45 In the following Tables VII and VIII which summarize the results obtained, the figure in the "dilution" column indicates the proportion (% by volume) of AMS 70% in the aqueous solution tested. 304L stainless steel DILUTION CORROSION SPEED (µm / year) Non additive AMS AMS additive 1 <5 <5 5 465 <5 10 331 <5 25 541 <5 50 398 <5 100 - 45 316L stainless steel DILUTION CORROSION SPEED (µm / year) Non additive AMS AMS additive 1 <5 <5 5 75 <5 10 157 <5 25 190 <5 50 160 <5 100 - 45

Claims (12)

Procédé pour protéger un acier inoxydable contre la corrosion par un acide organosulfonique, caractérisé en ce que l'on ajoute à la solution aqueuse dudit acide une quantité suffisante d'au moins un oxydant choisi parmi les sels ou oxydes de cérium (IV), de fer (III), de molybdène (VI) ou de vanadium (V), les nitrites et les persulfates.Method for protecting a stainless steel against corrosion by a organosulfonic acid, characterized in that said aqueous solution is added to the aqueous solution acid a sufficient amount of at least one oxidant chosen from salts or oxides cerium (IV), iron (III), molybdenum (VI) or vanadium (V), nitrites and persulfates. Procédé selon la revendication 1 dans lequel on utilise un nitrite alcalin, de préférence le nitrite de sodium.Process according to claim 1, in which an alkali nitrite is used, preferably sodium nitrite. Procédé selon la revendication 2, dans lequel la quantité de nitrite est comprise entre 1.10-4 et 1 mole/litre, de préférence entre 0,001 et 0,5 mole/litre.The method of claim 2, wherein the amount of nitrite is between 1.10 -4 and 1 mole / liter, preferably between 0.001 and 0.5 mole / liter. Procédé selon la revendication 1 dans lequel on utilise le cérium (IV) sous forme de sel double d'ammonium et de cérium (IV), de préférence le nitrate ou le sulfate d'ammonium et de cérium.Process according to Claim 1, in which the cerium (IV) is used under form of a double salt of ammonium and cerium (IV), preferably nitrate or ammonium and cerium sulfate. Procédé selon la revendication 4 dans lequel la concentration en ions Ce4+ est comprise entre 1.10-5 et 1.10-1 mole/litre, de préférence entre 1.10-4 et 5.10-2 mole/litre.Process according to Claim 4, in which the concentration of Ce 4+ ions is between 1.10 -5 and 1.10 -1 mole / liter, preferably between 1.10 -4 and 5.10 -2 mole / liter. Procédé selon la revendication 1 dans lequel on associe un sel de molybdène (VI), de préférence le molybdate de sodium, et un sel de cérium (IV), de préférence un sel double d'ammonium et de cérium (IV).Process according to Claim 1, in which a molybdenum salt is combined (VI), preferably sodium molybdate, and a cerium (IV) salt, preferably a double salt of ammonium and cerium (IV). Procédé selon la revendication 6 dans lequel chaque sel est utilisé en une quantité comprise entre 1.10-3 et 2.10-2 mole/litre, plus particulièrement entre 5.10-3 et 1.10-2 mole/litre.The method of claim 6 wherein each salt is used in an amount between 1.10 -3 and 2.10 -2 mole / liter, more particularly between 5.10 -3 and 1.10 -2 mole / liter. Procédé selon l'une des revendications 1 à 7, dans lequel l'acide organosulfonique est l'acide méthanesulfonique.Method according to one of claims 1 to 7, in which the organosulfonic acid is methanesulfonic acid. Solution aqueuse d'acide organosulfonique contenant au moins un oxydant choisi parmi les sels ou oxydes de cérium (IV), de fer (III), de molybdène (VI) ou de vanadium (V), les nitrites et les persulfates en une quantité suffisante pour que son potentiel spontané, mesuré au moyen d'une électrode en acier inoxydable, se situe dans la zone de passivité déterminée dans les mêmes conditions en l'absence dudit oxydant. Aqueous organosulfonic acid solution containing at least one oxidant chosen from the salts or oxides of cerium (IV), iron (III), molybdenum (VI) or of vanadium (V), nitrites and persulfates in an amount sufficient for its spontaneous potential, measured by means of a stainless steel electrode, is located in the passivity zone determined under the same conditions in the absence of said oxidant. Solution aqueuse selon la revendication 9 dans laquelle l'oxydant est un nitrite alcalin, de préférence le nitrite de sodium, ou un sel double d'ammonium et de cérium (IV), de préférence le nitrate ou le sulfate d'ammonium et de cérium.An aqueous solution according to claim 9 in which the oxidant is a alkali nitrite, preferably sodium nitrite, or a double salt of ammonium and cerium (IV), preferably nitrate or sulphate of ammonium and cerium. Solution aqueuse selon la revendication 9 contenant un sel de molybdène (VI), de préférence le molybdate de sodium, et un sel de cérium (IV), de préférence un sel double d'ammonium et de cérium (IV).An aqueous solution according to claim 9 containing a molybdenum salt (VI), preferably sodium molybdate, and a cerium (IV) salt, preferably a double salt of ammonium and cerium (IV). Solution aqueuse selon l'une des revendications 9 à 11 dans laquelle l'acide organosulfonique est l'acide méthanesulfonique.An aqueous solution according to one of claims 9 to 11 in which organosulfonic acid is methanesulfonic acid.
EP98403065A 1998-01-26 1998-12-07 Corrosion inhibiting of stainless steel in organic sulphonic acid Withdrawn EP0931854A1 (en)

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WO2019043339A1 (en) 2017-09-01 2019-03-07 Arkema France Sulfonic acid preparation method
WO2019043340A1 (en) * 2017-09-01 2019-03-07 Arkema France Metal corrosion inhibitors
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FR3070687A1 (en) * 2017-09-01 2019-03-08 Arkema France PROCESS FOR THE PREPARATION OF SULFONIC ACID
FR3070694A1 (en) * 2017-09-01 2019-03-08 Arkema France METAL CORROSION INHIBITORS
CN111051279A (en) * 2017-09-01 2020-04-21 阿科玛法国公司 Process for the preparation of sulfonic acids
US11040940B2 (en) 2017-09-01 2021-06-22 Arkema France Weakly coloured sulfonic acid
US11447450B2 (en) 2017-09-01 2022-09-20 Arkema France Process for producing sulfonic acid
CN111051279B (en) * 2017-09-01 2023-05-12 阿科玛法国公司 Process for the preparation of sulphonic acids
US11788192B2 (en) 2017-09-01 2023-10-17 Arkema France Inhibitors of metal corrosion

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