Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
  • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C309/04—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing only one sulfo group
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
  • C07C303/42—Separation; Purification; Stabilisation; Use of additives
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
  • C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
  • C07C309/06—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing halogen atoms, or nitro or nitroso groups bound to the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C309/29—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings
  • C07C309/30—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of non-condensed six-membered aromatic rings of six-membered aromatic rings substituted by alkyl groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
  • C07C309/01—Sulfonic acids
  • C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
  • C07C309/33—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of six-membered aromatic rings being part of condensed ring systems
  • C07C309/34—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton of six-membered aromatic rings being part of condensed ring systems formed by two rings
  • C07C309/35—Naphthalene sulfonic acids
• • 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
  • 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
  • C23F11/181—Nitrogen containing compounds

Definitions

• the present invention relates to the field of sulfonic acids and more particularly the field of weakly colored sulfonic acids, and their preparation process.
• Sulphonic acids and in particular so-called organic sulfonic acids, such as, for example, methanesulfonic acid (AMS), para-toluenesulfonic acid (APTS), benzenesulphonic acid (BS), ), trifluoromethanesulfonic acid are strong acids widely used in many applications, including catalysis and surface treatment, such as electroplating, stripping, cleaning, descaling, to name only the main ones of them, to limit themselves to it.
• AMS methanesulfonic acid
• APTS para-toluenesulfonic acid
• BS benzenesulphonic acid
• trifluoromethanesulfonic acid are strong acids widely used in many applications, including catalysis and surface treatment, such as electroplating, stripping, cleaning, descaling, to name only the main ones of them, to limit themselves to it.
• weakly corrosive sulfonic acids also known as “weak corrosion”
• weak corrosion have the disadvantage that they are colored more or less rapidly, depending on the nature of the sulphonic acid, the nitrite used, and the concentration of nitrite in said sulphonic acid.
• This coloration may be troublesome for the intended applications, particularly when the sulfonic acids are used as cleaning agents, as reaction catalysts for the manufacture of high value-added products, and others.
• the coloration may be considered as resulting from the presence of impurities which, in addition to polluting the sulphonic acid and rendering it unfit for the intended use, may at least render it incompatible with commercial specifications.
• This coloration therefore represents a major drawback for "weak corrosion" sulfonic acids, that is to say for sulfonic acids which include nitrites to make them weakly corrosive vis-à-vis metals and passivable alloys, iron, nickel, titanium, copper, aluminum, molybdenum, manganese, lead, and their alloys, as well as the pairs of these metals or alloys obtained by contact (crimping, riveting, bolting, welding, brazing), in particular with respect to stainless steels, and in particular common stainless steels (for example of the type AISI 304L and AISI 316L), but also more generally any stainless steel as defined in the standard NF EN 10088-1.
• sulfonic acids which include nitrites to make them weakly corrosive vis-à-vis metals and passivable alloys, iron, nickel, titanium, copper, aluminum, molybdenum, manganese, lead, and their alloys, as well as the pairs of these metals or
• a sulphonic acid is "colored" when its APHA color is strictly greater than 20.
• a weakly colored sulphonic acid in the sense of the present invention is a sulphonic acid which the color APHA is less than 20, preferably less than 15, more preferably less than 10, most preferably less than 5.
• the APHA color is a color standard named for the American Public Health Association and defined by ASTM D1209, and more specifically ASTM D1209-05 (201 1).
• the color APHA is a color scale, sometimes also called "yellowness index", which allows to evaluate the quality of liquids that are light to yellowish in color.
• the APHA color is measured using a colorimeter with a standard range from 0 to 200 APHA.
• a weak sulfonic acid corrosion according to the present invention remains in the passive state after application of a current of -800 ⁇ . ⁇ 2 , for 1 minute, while a sulfonic acid not in accordance with the present invention.
• the present invention (corrosive), returns to the active state (corrosion) after depassivation by application of said current amount of -800 ⁇ . ⁇ 2 for 1 minute.
• the low-corrosion sulphonic acids of the present invention are conventional sulphonic acids in which at least one nitrite has been added, and whose nitrite / sulphonic acid molar ratio is between 200 ppm and 6000 ppm, preferably between 400 ppm. and 2000 ppm, in particular between 500 ppm and 1900 ppm.
• conventional sulfonic acids may contain chloride ions in greater or lesser amounts.
• the presence and the quantity of chloride ions in the conventional sulphonic acids may result from many factors, among which the chlorine derivative (s) used in the process of manufacture of said conventional sulphonic acid itself, the chlorides or chlorinated derivatives present in the various solvents, additives, auxiliaries, fillers intended to formulate said sulphonic acid in order to facilitate its implementation, its use and its efficiency in the envisaged applications, and other.
• the present invention relates to a sulfonic acid comprising:
• APHA color is less than 20, preferably less than 15, more preferably less than 10, most preferably less than 5.
• sulfonic acid any sulfonic acid known to those skilled in the art and more particularly the sulfonic acids of formula R-SO3H, where R represents a saturated or unsaturated hydrocarbon chain, linear, branched or cyclic , having 1 to 12 carbon atoms, substituted or unsubstituted by one or more radicals and / or atoms selected from halogen atoms (such as fluorine, chlorine, bromine), alkyl radicals containing from 1 to 6 carbon atoms, carbon and 6 or 10-membered aryl and heteroaryl radicals.
• R represents a saturated or unsaturated hydrocarbon chain, linear, branched or cyclic , having 1 to 12 carbon atoms, substituted or unsubstituted by one or more radicals and / or atoms selected from halogen atoms (such as fluorine, chlorine, bromine), alkyl radicals containing from 1 to 6 carbon atoms, carbon and 6 or 10-membered aryl and hetero
• alkyl is meant a saturated hydrocarbon radical, linear or branched.
• aryl is meant an aromatic radical, preferably phenyl or naphthyl, more preferably phenyl.
• heteroaryl is meant an aromatic radical having one or more heteroatoms selected from oxygen, nitrogen and sulfur.
• R is a hydrocarbon chain having 1 to 6 carbon atoms, more preferably selected from methyl, ethyl, n-propyl, / 'so-propyl, n-butyl, /' so-butyl, sec-butyl tert-butyl, linear or branched pentyl radicals, linear or branched hexyl radicals, and phenyl and naphthyl radicals.
• the sulphonic acids included in the context of the present invention are preferably selected from methanesulfonic acid, ethanesulfonic acid, n-propanesulfonic acid, propane-sulfonic isophthalic acid, n-butane-sulfonic acid, / 'n-butane-sulfonic acid, sec-butane-sulphonic acid, tert-butane-sulphonic acid, trifluoromethanesulfonic acid, para-toluenesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid and mixtures of two or more of them in all proportions.
• the sulphonic acid used in the context of the present invention is methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulphonic acid or para-toluenesulphonic acid.
• the sulfonic acid is methanesulfonic acid.
• the sulfonic acid used in the context of the present invention may be sulfonic acid alone or in a mixture of two or more sulfonic acids, optionally in a solvent medium and optionally in admixture with one or more additives and / or fillers. known to those skilled in the art.
• the sulfonic acid (s) may be in a solvent medium, said solvent may be water or an organic solvent or a mixture of organic solvents, or water mixed with one or more other organic solvents.
• concentration of sulphonic acid (s) in the solvent (s) is between 0.01% and 100%, inclusive limits, by weight of sulphonic acid (s) relative to the total weight of sulfonic acid (s) in a solvent medium, it being understood that when the concentration is equal to 100%, the amount of solvent is zero or negligible or non-detectable.
• this concentration is between 0.01% and 99.99%, preferably between 0.1% and 99.9%, more preferably between 0.5% and 75%, limits included, by weight of sulfonic acid (s) relative to the total weight of sulfonic acid (s) in a solvent medium.
• organic solvents indicated above and used to solvanter the (s) sulfonic acid (s) may be of any type known to those skilled in the art, and preferably the water-soluble organic solvents.
• water-soluble organic solvents such as alcohols, sulphoxides, mineral or organic acids, more preferably the methanol, ethanol, dimethylsulfoxide, sulfuric acid, to name only the most common and well known of them.
• the additives and fillers that may be present in admixture with the sulphonic acids may for example be, without limitation, one or more additives and / or fillers chosen from viscosity or rheology modifiers, foaming agents, anti-foaming agents, surfactants, disinfectants, biocides, stabilizers, oxidizing agents, enzymes, pigments, dyes, flame retardants, flame retardants, fragrances, flavors, and others.
• nitrite in the proportions indicated above can be carried out according to any method known to those skilled in the art, in particular by adding one or more nitrite (s) of alkali metal or alkaline earth metal, in solid form or dissolved in a solvent, such as water.
• a solvent such as water.
• the amount of chlorides present in the sulfonic acid can be easily controlled and adjusted depending on the nature of the sulfonic acid production process itself, its degree of purity, which can be improved according to one or several techniques known to those skilled in the art, such as distillation, recrystallization, and others.
• the amount of chlorides present in the sulfonic acid can be easily controlled and adjusted depending on the nature of the potential solvent (s), additives and fillers added thereto. Those skilled in the art will readily understand that a sulphonic acid with a low chloride content will see this content increased, if it is decided, for example, to dilute said sulphonic acid in water with a high concentration of chloride or to add a charge. such as a salt containing chlorides.
• the low-corrosion sulfonic acid according to the present invention thus has an APHA color is less than 20, preferably less than 15, more particularly less than 10, especially less than 5, that is to say a absence or almost no color, which makes it possible to have a low-corrosion sulfonic acid, thus satisfying most or all commercial specifications, in a very large number of fields of application.
• the present invention also relates to a composition
• a composition comprising at least one sulphonic acid as defined above, a solvent as defined above, preferably water, and optionally one or more additive (s) and / or load (s) as defined above.
• AMS methanesulfonic acid
• sample 4 chloride / AMS molar ratio equal to 220 ppm.
• the flask is immediately closed hermetically and the whole is placed under agitation (400 rpm) for 1 hour at 20 ° C. Nitrogen is then bubbled into the solution (flow rate 10 mL.mn- 1 ) for 360 minutes.
• the color of each sample is then measured using a colorimeter LICO 620 from the company HACH, with a standard range between 0 and 200 APHA.
• the apparatus is previously calibrated with standard solutions ranging from 0 to 200 APHA.
• a sample of 4 mL of the solution whose color is to be determined is introduced into a cuvette provided by Hach and the color is read automatically on the device.
• the AMS / inhibitor mixture is colorless
• the APHA value is greater than 20 and the methanesulfonic acid is colored.
• the measurement of the amount of chlorides present in a sulfonic acid is carried out by argentimetry using a potentiometer equipped with a silver sulfide electrode sold by the company Metrohm AG under the reference 6.0404.100.
• Nitrites can be determined by any method known to those skilled in the art and for example by ion chromatography.
• the samples to be tested are diluted approximately 150 times (0.6 g of sample and then 100 ml supplement with ultrapure water) and passed on an ICS5000 device from the company Dionex TM.
• the detection mode is the conductimetry and the results are read against a previously established calibration curve.
• the calibration range is prepared from standards of nitrites, as well as an AMS matrix.
• Commercial standards of nitrites 1000 mg.L -1 in water, supplier CPA) 1, 10 and 100 mg.L "1 solutions are prepared by diluting them in ultra pure water.
• the AMS matrix is made from a commercial solution of 70% AMS (Sigma-Aldrich) diluted in ultra pure water. To do this, 0.6 g of 70% AMS is weighed into a 100 ml volumetric flask, and then complete with ultra pure water.
• reference electrode saturated calomel electrode or "ECS"
• working electrode 304L stainless steel test specimen of size 1 cm 2 .
• test piece of the material to be tested is polished with abrasive paper P400 and then passivated for 1 hour in a 10% nitric acid solution at room temperature. This allows an identical starting state for all tests.
• the temperature of the test is thermostated at 20 ° C ⁇ 2 ° C.
• the applied protocol comprises the following three steps:
• the behavior is completely different in a 70% solution by weight in water of a methanesulfonic acid additive nitrites.
• methanesulfonic acid added with sodium nitrite is a weak methane-sulfonic acid corrosion in the sense of the present invention.

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• 2017
  • 2017-09-01 FR FR1758098A patent/FR3070686B1/fr active Active
• 2018
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