FR2672058A1 - Composition inhibiting the corrosion of ferrous metals, process for its manufacture and its use - Google Patents
Composition inhibiting the corrosion of ferrous metals, process for its manufacture and its use Download PDFInfo
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- FR2672058A1 FR2672058A1 FR9100817A FR9100817A FR2672058A1 FR 2672058 A1 FR2672058 A1 FR 2672058A1 FR 9100817 A FR9100817 A FR 9100817A FR 9100817 A FR9100817 A FR 9100817A FR 2672058 A1 FR2672058 A1 FR 2672058A1
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- FR
- France
- Prior art keywords
- sodium
- nitrite
- perborate
- composition according
- molybdate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 40
- 230000007797 corrosion Effects 0.000 title claims description 16
- 238000005260 corrosion Methods 0.000 title claims description 16
- 229910052751 metal Inorganic materials 0.000 title claims description 14
- 239000002184 metal Substances 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- -1 ferrous metals Chemical class 0.000 title claims description 7
- 238000000034 method Methods 0.000 title claims description 7
- 230000002401 inhibitory effect Effects 0.000 title claims description 3
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 67
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 33
- 229960001922 sodium perborate Drugs 0.000 claims abstract description 30
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 27
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 20
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 20
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910021538 borax Inorganic materials 0.000 claims abstract description 6
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 6
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000011550 stock solution Substances 0.000 claims description 18
- 235000010234 sodium benzoate Nutrition 0.000 claims description 14
- 239000004299 sodium benzoate Substances 0.000 claims description 14
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 13
- 239000001509 sodium citrate Substances 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 11
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 10
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 claims description 10
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 5
- 235000011083 sodium citrates Nutrition 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 3
- 229940038773 trisodium citrate Drugs 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 238000003754 machining Methods 0.000 claims description 2
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 claims 1
- 229940043264 dodecyl sulfate Drugs 0.000 claims 1
- 229910000831 Steel Inorganic materials 0.000 abstract description 9
- 239000010959 steel Substances 0.000 abstract description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- 239000003112 inhibitor Substances 0.000 description 4
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 3
- 239000010413 mother solution Substances 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- 239000004141 Sodium laurylsulphate Substances 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003889 eye drop Substances 0.000 description 1
- 229940012356 eye drops Drugs 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000003352 sequestering agent Substances 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- 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
- C23F11/185—Refractory metal-containing compounds
-
- 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
- C23F11/187—Mixtures of inorganic inhibitors
Abstract
Description
Composition d'inhibiteur de la corrosion des métaux ferreux, procédé pour sa préparation, et son utilisation
L'invention concerne la protection contre la corrosion des métaux ferreux, en particulier du fer e-t des aciers.Ferrous metal corrosion inhibitor composition, process for its preparation, and use thereof
The invention relates to the protection against corrosion of ferrous metals, in particular iron and steels.
On connaît des compositions aqueuses d'inhibiteur de la corrosion des métaux ferreux, utilisées notamment pour le refroidissement de pièces en acier telles que les tôles ou les tubes au cours de leur fabrication, en vue de protéger ces pièces contre la corrosion, tant en cours de fabrication que pendant leur stockage. Ces produits peuvent également servir à la protection de canalisations en acier, dans les circuits de refroidissement fermés, ou comme additifs à l'eau de refroidissement d'installation de coupe des métaux.Aqueous compositions of inhibitor of corrosion of ferrous metals are known, used in particular for cooling steel parts such as sheets or tubes during their manufacture, with a view to protecting these parts against corrosion, both in progress of manufacturing only during their storage. These products can also be used for the protection of steel pipes, in closed cooling circuits, or as additives to cooling water for metal cutting installations.
Ces compositions connues, pour être efficaces, contiennent une quantité élevée de nitrite de sodium et présentent donc une forte toxicité.These known compositions, to be effective, contain a high amount of sodium nitrite and therefore have a high toxicity.
Le but de l'invention est de réduire la quantité de nitrite de sodium, voire de remplacer complètement ce composé par des produits non toxiques.The object of the invention is to reduce the amount of sodium nitrite, or even to completely replace this compound with non-toxic products.
L'invention vise une composition aqueuse d'inhibiteur de la corrosion des métaux ferreux caractérisée en ce qu'elle contient au moins un agent passivant choisi parmi le nitrite de sodium, le molybdate de sodium et le perborate de sodium, et du borate de sodium comme agent de pH, la concentration de nitrite de sodium étant comprise entre 2 et 5 g/l lors qutil est utilisé comme seul agent passivant, entre 0,5 et 1 g/l lorsqu'il est associé au molybdate de sodium et entre 1 et 2 g/l lorsqu'il est associé au perborate de sodium, la concentration de molybdate de sodium étant de 3 g/l environ lorsqu'il est utilisé comme seul agent passivant, et comprise entre 0,5 et 1 g/l lorsqu'il est associé au nitrite de sodium ou au perborate de sodium, la concentration de perborate de sodium étant comprise entre 2 et 4 g/l lorsqu'il est utilisé comme seul agent passivant, entre 1 et 2 g/l lorsqu'il est associé au nitrite de sodium et entre 3 et 4 g/l lorsqu'il est associé au molybdate de sodium, et la concentration de l'agent de pH étant comprise entre 1 et 2 g/l de borate de sodium décahydraté, de telle sorte que le pH soit supérieur à 8,5.The invention relates to an aqueous composition for inhibiting corrosion of ferrous metals, characterized in that it contains at least one passivating agent chosen from sodium nitrite, sodium molybdate and sodium perborate, and sodium borate. as a pH agent, the concentration of sodium nitrite being between 2 and 5 g / l when it is used as the sole passivating agent, between 0.5 and 1 g / l when it is combined with sodium molybdate and between 1 and 2 g / l when combined with sodium perborate, the sodium molybdate concentration being approximately 3 g / l when used as the sole passivating agent, and between 0.5 and 1 g / l when '' it is associated with sodium nitrite or sodium perborate, the concentration of sodium perborate being between 2 and 4 g / l when used as sole passivating agent, between 1 and 2 g / l when it is associated with sodium nitrite and between 3 and 4 g / l when associated with molybdate sodium, and the concentration of the pH agent being between 1 and 2 g / l of sodium borate decahydrate, so that the pH is greater than 8.5.
Dans cette composition, le rôle de l'agent passivant est de former à la surface du métal une couche d'oxyde adhérente et protectrice, et l'agent de pH permet à l'agent passivant d'opérer dans des conditions d'efficacité maximale. Les compositions contenant à la fois du perborate de sodium et du molybdate de sodium sont supérieures en efficacité à celles contenant seulement du perborate.In this composition, the role of the passivating agent is to form an adherent and protective oxide layer on the surface of the metal, and the pH agent allows the passivating agent to operate under conditions of maximum efficiency. . Compositions containing both sodium perborate and sodium molybdate are more effective than those containing only perborate.
Dans certains cas, la composition peut contenir en outre l'un au moins des additifs suivants, aux concentrations suivantes en g/l citrate trisodique 0,25 à 0,75 benzoate de sodium 1 à 2 laurysulfate de sodium 0,05 à 0,133
Le citrate trisodique est un agent séquestrant non toxique, dont la présence est avantageuse lorsque l'eau présente une teneur élevée en ions calcium. I1 évite les dépôts calcaires qui sont préjudiciables à l'aspect des pièces telles que tubes et tôles qu'on veut protéger temporairement contre la corrosion atmosphérique, ou qui peuvent initier une corrosion par crevasses dans un circuit de refroidissement.In certain cases, the composition may also contain at least one of the following additives, at the following concentrations in g / l trisodium citrate 0.25 to 0.75 sodium benzoate 1 to 2 sodium laurysulfate 0.05 to 0.133
Trisodium citrate is a non-toxic sequestering agent, the presence of which is advantageous when the water has a high content of calcium ions. I1 avoids lime deposits which are detrimental to the appearance of parts such as tubes and sheets which are to be temporarily protected against atmospheric corrosion, or which can initiate crevice corrosion in a cooling circuit.
Le benzoate de sodium renforce l'action de l'inhibiteur dans le cas de pièces soumises à des conditions de corrosion atmosphérique sévères, dues par exemple à d'importantes et fréquentes variations de température et de degré hygrométrique.Sodium benzoate enhances the action of the inhibitor in the case of parts subjected to severe atmospheric corrosion conditions, due for example to large and frequent variations in temperature and humidity.
Le laurylsulfate de sodium est un agent tensio-actif qui favorise le mouillage des pièces à protéger par la solution.Sodium lauryl sulfate is a surfactant which promotes the wetting of the parts to be protected by the solution.
I1 est préférable de l'utiliser lorsque la durée de séjour des pièces dans celle-ci est très limitée, et notamment lorsque leur forme n'est pas plane. It is preferable to use it when the duration of stay of the parts in it is very limited, and in particular when their shape is not planar.
Par ailleurs, l'addition de 1 à 2 g/l de monohydrogénophosphate de sodium augmente l'efficacité des solutions inhibitrices en formant un phosphate de fer insoluble à la surface des pièces. Son usage dans les solutions contenant du perborate de sodium permet de compenser l'efficacité moindre de cet agent passivant, lorsqu'il nTest pas associé au nitrite de sodium. On peut ainsi s'affranchir des problèmes toxicologiques posés par le nitrite, en cas de contact du personnel avec la solution.Furthermore, the addition of 1 to 2 g / l of sodium monohydrogen phosphate increases the effectiveness of the inhibitor solutions by forming an insoluble iron phosphate on the surface of the parts. Its use in solutions containing sodium perborate makes it possible to compensate for the reduced effectiveness of this passivating agent, when it is not associated with sodium nitrite. We can thus get rid of the toxicological problems posed by nitrite, in the event of personnel contact with the solution.
Des concentrations préférentielles pour les différents constituants autres que l'hydrogénophosphate de sodium sont données ci-après (en g/l) nitrite de sodium seul 3 à 4 perborate de sodium seul 3 à 4 nitrite de sodium 0,5 à 1 + molybdate de sodium 0,5 à 1 nitrite de sodium 1 à 2 + perborate de sodium 1 à 2 borate de sodium décahydraté 1 environ citrate de sodium 0,5 environ benzoate de sodium 1,5 environ laurysulfate de sodium 0,1 environ.Preferred concentrations for the various constituents other than sodium hydrogen phosphate are given below (in g / l) sodium nitrite alone 3 to 4 sodium perborate alone 3 to 4 sodium nitrite 0.5 to 1 + molybdate sodium 0.5 to 1 sodium nitrite 1 to 2 + sodium perborate 1 to 2 sodium borate decahydrate 1 approximately sodium citrate 0.5 approximately sodium benzoate 1.5 approximately sodium laurysulfate 0.1 approximately.
L'invention vise également un procédé pour préparer une composition telle que définie ci-dessus, dans lequel on dilue une première solution-mère concentrée contenant le ou les agents passivants et le cas échéant le monohydrogénophosphate de sodium, et qu'on y ajoute une seconde solutionmère concentrée contenant les autres constituants de la composition, les concentrations maximales des différents constituants dans les solutions-mères étant les suivantes en g/l nitrite de sodium seul 750 molybdate de sodium seul 450 perborate de sodium seul 600 nitrite de sodium 150 + molybdate de sodium 150 nitrite de sodium 300 + perborate de sodium 300 perborate de sodium 600 + molybdate de sodium 150 monohydrogénophosphate de sodium 300 borate de sodium décahydraté 75 citrate de sodium 28 benzoate de sodium 75 laurysulfate de sodium 5
Ces concentrations maximales sont 150 fois plus élevées pour la première solution-mère et 37,5 fois plus élevées pour la seconde solution-mère que les concentrations maximales des mêmes constituants dans les compositions d'application, ce qui indique que le rapport de dilution peut atteindre 150 et 37t5 respectivement pour les deux solutionsmères.The invention also relates to a process for preparing a composition as defined above, in which a first concentrated stock solution containing the passivating agent (s) and if necessary the sodium monohydrogenphosphate is diluted, and a second concentrated mother solution containing the other constituents of the composition, the maximum concentrations of the various constituents in the mother solutions being the following in g / l sodium nitrite alone 750 sodium molybdate alone 450 sodium perborate alone 600 sodium nitrite 150 + molybdate sodium 150 sodium nitrite 300 + sodium perborate 300 sodium perborate 600 + sodium molybdate 150 sodium monohydrogen phosphate 300 sodium borate decahydrate 75 sodium citrate 28 sodium benzoate 75 sodium laurysulfate 5
These maximum concentrations are 150 times higher for the first stock solution and 37.5 times higher for the second stock solution than the maximum concentrations of the same constituents in the application compositions, which indicates that the dilution ratio can reach 150 and 37t5 respectively for the two mother solutions.
L'invention a également pour objet une solution-mère pour la mise en oeuvre du procédé qui vient d'être défini, contenant au moins un agent passivant choisi parmi le nitrite de sodium, le molybdate de sodium et le perborate de sodium, et le cas échéant du monohydrogénophosphate de sodium, ainsi qu'une solution-mère pour la mise en oeuvre du même procédé, contenant du borate de sodium décahydraté et au moins un additif choisi parmi le citrate de sodium, le benzoate de sodium et le laurylsulfate de sodium, les concentrations dans ces deux solutions-mères ne dépassant pas celles qui viennent d'être indiquées.The invention also relates to a stock solution for implementing the process which has just been defined, containing at least one passivating agent chosen from sodium nitrite, sodium molybdate and sodium perborate, and if necessary sodium monohydrogen phosphate, as well as a stock solution for the implementation of the same process, containing sodium borate decahydrate and at least one additive chosen from sodium citrate, sodium benzoate and sodium lauryl sulphate , the concentrations in these two stock solutions not exceeding those which have just been indicated.
Compte tenu de la faible solubilité du perborate de sodium, la solution-mère contenant ce composé est en réalité une suspension. Celui-ci passe totalement. en solution lors de la dilution.Given the low solubility of sodium perborate, the stock solution containing this compound is actually a suspension. This one passes completely. in solution during dilution.
La composition selon l'invention peut être utilisée pour la protection contre la corrosion de pièces en métaux ferreux exposées à l'atmosphère, lesdites pièces étant immergées dans ladite composition avant exposition à l'atmosphère, ou bien pour le refroidissement de pièces en métaux ferreux lors de leur fabrication, notamment par formage ou par usinage.The composition according to the invention can be used for the protection against corrosion of ferrous metal parts exposed to the atmosphere, said parts being immersed in said composition before exposure to the atmosphere, or else for cooling ferrous metal parts during their manufacture, in particular by forming or machining.
Dans ce dernier cas, le refroidissement peut être réalisé soit d'abord au moyen d'eau non traitée, puis au moyen de la composition selon l'invention, soit entièrement au moyen de cette composition, laquelle peut alors être portée jusqu là une température de 80"C sans diminution notable dans son efficacité.In the latter case, the cooling can be carried out either first by means of untreated water, then by means of the composition according to the invention, or entirely by means of this composition, which can then be brought to a temperature 80 "C without any noticeable decrease in its efficiency
Pour ces applications, on utilise avantageusement une solution contenant comme agent passivant du nitrite de sodium, soit seul, soit associé au molybdate de sodium ou au perborate de sodium, ou une solution contenant du perborate de sodium comme seul agent passivant, additionné d'hydrogénophosphate de sodium, ces solutions contenant également du borate de sodium, du citrate de sodium et du benzoate de sodium et présentant les concentrations préférées indiquées ci-dessus.For these applications, it is advantageous to use a solution containing as passivating agent sodium nitrite, either alone or in combination with sodium molybdate or sodium perborate, or a solution containing sodium perborate as sole passivating agent, supplemented with hydrogen phosphate. sodium, these solutions also containing sodium borate, sodium citrate and sodium benzoate and having the preferred concentrations indicated above.
Les pièces traitées sont protégées contre la corrosion pendant deux mois au moins, en l'absence de contact avec des eaux de ruissellement. The treated parts are protected against corrosion for at least two months, in the absence of contact with surface water.
La composition selon l'invention est également utilisable en tant que fluide circulant dans un circuit fermé, notamment un circuit de refroidissement, comportant des éléments en métaux ferreux, notamment des canalisations en acier.The composition according to the invention can also be used as a fluid circulating in a closed circuit, in particular a cooling circuit, comprising elements made of ferrous metals, in particular steel pipes.
b
Dans ce cas, la composition contient avantageusement du nitrite de sodium ou du perborate de sodium comme seul agent passivant, ainsi que du borate de sodium décahydraté, du citrate de sodium, du benzoate de sodium et du laurylsulfate de sodium, aux concentrations préférées indiquées ci-dessus.b
In this case, the composition advantageously contains sodium nitrite or sodium perborate as sole passivating agent, as well as sodium borate decahydrate, sodium citrate, sodium benzoate and sodium lauryl sulphate, at the preferred concentrations indicated below. -above.
Les éléments à protéger étant en contact permanent avec la solution, il n'est pas nécessaire d'ajouter du monohydrogénophosphate de sodium au perborate de sodium.The elements to be protected being in permanent contact with the solution, it is not necessary to add sodium monohydrogenphosphate to sodium perborate.
La plupart des constituants de la composition selon l'invention, notamment lorsqu'elle ne contient pas de nitrite de sodium, présentent un risque très limité en matière de toxicité. En particulier, certains d'entre eux sont utilisés dans l'industrie pharmaceutique pour la fabrication de médicaments (benzoate de sodium pour les sirops, borate de sodium et laurylsulfate de sodium pour les collyres), dans l'industrie alimentaire (citrate de sodium) et dans les lessives (perborate de sodium).Most of the constituents of the composition according to the invention, in particular when it does not contain sodium nitrite, present a very limited risk as regards toxicity. In particular, some of them are used in the pharmaceutical industry for the manufacture of medicines (sodium benzoate for syrups, sodium borate and sodium lauryl sulfate for eye drops), in the food industry (sodium citrate) and in detergents (sodium perborate).
Dans les compositions contenant du nitrite, l'association de celui-ci notamment avec le molybdate de sodium, le benzoate et le borate de sodium, provoque un effet synergique qui permet de limiter la teneur en nitrite de sodium à 4 à 5 g/l de solution, au lieu de teneurs de l'ordre de 10 g/l pour certaines formulations à base de nitrites actuellement commercialisées.In the compositions containing nitrite, the association of this one in particular with sodium molybdate, benzoate and sodium borate, causes a synergistic effect which makes it possible to limit the content of sodium nitrite to 4 to 5 g / l of solution, instead of contents of the order of 10 g / l for certain formulations based on nitrites currently marketed.
Des études en laboratoire ont été effectuées par des techniques électrochimiques pour déterminer d'une part l'efficacité des compositions selon l'invention (mesure des courants de corrosion de l'acier immergé dans les solutions, en comparaison avec les résultats obtenus dans de l'eau de ville), d'autre part le mécanisme de l'inhibition (tracé de courbes de polarisation).Laboratory studies were carried out by electrochemical techniques to determine on the one hand the effectiveness of the compositions according to the invention (measurement of the corrosion currents of the steel immersed in the solutions, in comparison with the results obtained in l city water), on the other hand the mechanism of inhibition (drawing of polarization curves).
On a ainsi constaté que l'utilisation de ces solutions permet de réduire de plusieurs ordres de grandeur la vitesse de corrosion de l'acier dans les conditions suivantes - immersion de longue durée dans l'eau de ville, - immersion temporaire puis stockage à l'air dans des conditions de température et d'hygrométrie variables.It has thus been found that the use of these solutions makes it possible to reduce the corrosion rate of steel by several orders of magnitude under the following conditions - long-term immersion in tap water, - temporary immersion then storage at air under variable temperature and humidity conditions.
Exemple
On réalise trois solutions-mères Al, A2 et B présentant les compositions suivantes en g/l
Solution-mère Al nitrite de sodium 450
Solution-mère A2 nitrite de sodium 75 molybdate de sodium 150
Solution-mère B borate de sodium décahydraté 38 citrate de sodium 18 benzoate de sodium 60 laurylsulfate de sodium 3,5.Example
Three stock solutions A1, A2 and B are produced having the following compositions in g / l
Stock solution Al sodium nitrite 450
Stock solution A2 sodium nitrite 75 sodium molybdate 150
Stock solution B sodium borate decahydrate 38 sodium citrate 18 sodium benzoate 60 sodium lauryl sulfate 3.5.
On prépare deux solutions d'application en diluant un volume de solution-mère Al et un volume de solution-mère A2, respec tivement, par 145 volumes d'eau de ville, et en y ajoutant 4 volumes de solution-mère B.Two application solutions are prepared by diluting one volume of stock solution A1 and one volume of stock solution A2, respectively, by 145 volumes of tap water, and by adding 4 volumes of stock solution B.
On immerge des tubes en acier, en fin de fabrication, dans l'une ou l'autre de ces solutions pendant une durée de 8 secondes, puis on les égoutte et on les entrepose dans un hall couvert, avec contrôle périodique de l'état de surface.Steel tubes are immersed, at the end of manufacture, in one or the other of these solutions for a period of 8 seconds, then they are drained and stored in a covered hall, with periodic status checks of surface.
On constate que les tubes ainsi traités sont préservés de toute corrosion, localisée ou généralisée, pendant une durée d'au moins trois mois. Par ailleurs, ce traitement ne nuit pas à l'accrochage des revêtements protecteurs qui peuvent être appliqués ultérieurement sur la surface des tubes.It can be seen that the tubes thus treated are preserved from any corrosion, localized or generalized, for a period of at least three months. Furthermore, this treatment does not harm the attachment of protective coatings which can be applied subsequently to the surface of the tubes.
Les mêmes solutions sont également mises en oeuvre par arrosage de tubes en acier du début à la fin de la chaîne de fabrication. La soudure des tubes provoquant une élévation de la température des solutions, on a pu vérifier que l'efficacité de celle-ci n'était pas affectée jusqu'à 70" environ.The same solutions are also implemented by sprinkling steel tubes from the start to the end of the production line. The welding of the tubes causing an increase in the temperature of the solutions, it was possible to verify that the efficiency of the latter was not affected up to approximately 70 ".
Cependant, pour des raisons pratiques, en particulier pour éviter la dilatation pouvant entraîner des arrêts de production, on préfère adjoindre au circuit d'arrosage un système de refroidissement.However, for practical reasons, in particular to avoid expansion which can lead to production stoppages, it is preferable to add a cooling system to the sprinkler circuit.
Les résultats ainsi enregistrés sont équivalents ou supérieurs à ceux des compositions du commerce contenant des concentrations en nitrite de sodium de l'ordre de 10 g/l. The results thus recorded are equivalent or superior to those of the commercial compositions containing concentrations of sodium nitrite of the order of 10 g / l.
Claims (13)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9100817A FR2672058B1 (en) | 1991-01-24 | 1991-01-24 | COMPOSITION OF FERROUS METAL CORROSION INHIBITOR, PROCESS FOR PREPARING THE SAME, AND USE THEREOF. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9100817A FR2672058B1 (en) | 1991-01-24 | 1991-01-24 | COMPOSITION OF FERROUS METAL CORROSION INHIBITOR, PROCESS FOR PREPARING THE SAME, AND USE THEREOF. |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| FR2672058A1 true FR2672058A1 (en) | 1992-07-31 |
| FR2672058B1 FR2672058B1 (en) | 1995-04-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| FR9100817A Expired - Fee Related FR2672058B1 (en) | 1991-01-24 | 1991-01-24 | COMPOSITION OF FERROUS METAL CORROSION INHIBITOR, PROCESS FOR PREPARING THE SAME, AND USE THEREOF. |
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| FR (1) | FR2672058B1 (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001098558A2 (en) * | 2000-06-22 | 2001-12-27 | United States Filter Corporation | Corrosion control utilizing a hydrogen peroxide donor |
| US6503305B1 (en) * | 2000-05-18 | 2003-01-07 | Hammond Group, Inc. | Non-toxic corrosion inhibitor |
| US6716359B1 (en) | 2000-08-29 | 2004-04-06 | United States Filter Corporation | Enhanced time-based proportional control |
| US6776926B2 (en) | 2001-08-09 | 2004-08-17 | United States Filter Corporation | Calcium hypochlorite of reduced reactivity |
| US8591730B2 (en) | 2009-07-30 | 2013-11-26 | Siemens Pte. Ltd. | Baffle plates for an ultraviolet reactor |
| US8652336B2 (en) | 2006-06-06 | 2014-02-18 | Siemens Water Technologies Llc | Ultraviolet light activated oxidation process for the reduction of organic carbon in semiconductor process water |
| US8741155B2 (en) | 2007-04-03 | 2014-06-03 | Evoqua Water Technologies Llc | Method and system for providing ultrapure water |
| US8753522B2 (en) | 2007-04-03 | 2014-06-17 | Evoqua Water Technologies Llc | System for controlling introduction of a reducing agent to a liquid stream |
| US8877067B2 (en) | 2011-05-26 | 2014-11-04 | Evoqua Water Technologies Llc | Method and arrangement for a water treatment |
| US8961798B2 (en) | 2007-04-03 | 2015-02-24 | Evoqua Water Technologies Llc | Method for measuring a concentration of a compound in a liquid stream |
| US9365435B2 (en) | 2007-04-03 | 2016-06-14 | Evoqua Water Technologies Llc | Actinic radiation reactor |
| US9365436B2 (en) | 2007-04-03 | 2016-06-14 | Evoqua Water Technologies Llc | Method of irradiating a liquid |
| US9725343B2 (en) | 2007-04-03 | 2017-08-08 | Evoqua Water Technologies Llc | System and method for measuring and treating a liquid stream |
| US10343939B2 (en) | 2006-06-06 | 2019-07-09 | Evoqua Water Technologies Llc | Ultraviolet light activated oxidation process for the reduction of organic carbon in semiconductor process water |
| US10494281B2 (en) | 2015-01-21 | 2019-12-03 | Evoqua Water Technologies Llc | Advanced oxidation process for ex-situ groundwater remediation |
| US11161762B2 (en) | 2015-01-21 | 2021-11-02 | Evoqua Water Technologies Llc | Advanced oxidation process for ex-situ groundwater remediation |
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| US6620315B2 (en) | 2001-02-09 | 2003-09-16 | United States Filter Corporation | System for optimized control of multiple oxidizer feedstreams |
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|---|---|---|---|---|
| US6503305B1 (en) * | 2000-05-18 | 2003-01-07 | Hammond Group, Inc. | Non-toxic corrosion inhibitor |
| WO2001098558A2 (en) * | 2000-06-22 | 2001-12-27 | United States Filter Corporation | Corrosion control utilizing a hydrogen peroxide donor |
| WO2001098558A3 (en) * | 2000-06-22 | 2002-07-04 | United States Filter Corp | Corrosion control utilizing a hydrogen peroxide donor |
| US6716359B1 (en) | 2000-08-29 | 2004-04-06 | United States Filter Corporation | Enhanced time-based proportional control |
| US6776926B2 (en) | 2001-08-09 | 2004-08-17 | United States Filter Corporation | Calcium hypochlorite of reduced reactivity |
| US10550020B2 (en) | 2006-06-06 | 2020-02-04 | Evoqua Water Technologies Llc | Ultraviolet light activated oxidation process for the reduction of organic carbon in semiconductor process water |
| US8652336B2 (en) | 2006-06-06 | 2014-02-18 | Siemens Water Technologies Llc | Ultraviolet light activated oxidation process for the reduction of organic carbon in semiconductor process water |
| US10343939B2 (en) | 2006-06-06 | 2019-07-09 | Evoqua Water Technologies Llc | Ultraviolet light activated oxidation process for the reduction of organic carbon in semiconductor process water |
| US8753522B2 (en) | 2007-04-03 | 2014-06-17 | Evoqua Water Technologies Llc | System for controlling introduction of a reducing agent to a liquid stream |
| US8961798B2 (en) | 2007-04-03 | 2015-02-24 | Evoqua Water Technologies Llc | Method for measuring a concentration of a compound in a liquid stream |
| US9365435B2 (en) | 2007-04-03 | 2016-06-14 | Evoqua Water Technologies Llc | Actinic radiation reactor |
| US9365436B2 (en) | 2007-04-03 | 2016-06-14 | Evoqua Water Technologies Llc | Method of irradiating a liquid |
| US9725343B2 (en) | 2007-04-03 | 2017-08-08 | Evoqua Water Technologies Llc | System and method for measuring and treating a liquid stream |
| US9764968B2 (en) | 2007-04-03 | 2017-09-19 | Evoqua Water Technologies Llc | Method and system for providing ultrapure water |
| US8741155B2 (en) | 2007-04-03 | 2014-06-03 | Evoqua Water Technologies Llc | Method and system for providing ultrapure water |
| US8591730B2 (en) | 2009-07-30 | 2013-11-26 | Siemens Pte. Ltd. | Baffle plates for an ultraviolet reactor |
| US8877067B2 (en) | 2011-05-26 | 2014-11-04 | Evoqua Water Technologies Llc | Method and arrangement for a water treatment |
| US10494281B2 (en) | 2015-01-21 | 2019-12-03 | Evoqua Water Technologies Llc | Advanced oxidation process for ex-situ groundwater remediation |
| US11161762B2 (en) | 2015-01-21 | 2021-11-02 | Evoqua Water Technologies Llc | Advanced oxidation process for ex-situ groundwater remediation |
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| FR2672058B1 (en) | 1995-04-28 |
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