US2853364A - Method of inhibiting the corrosiveness of aqueous solutions of sodium bisulfate towards stainless steels - Google Patents
Method of inhibiting the corrosiveness of aqueous solutions of sodium bisulfate towards stainless steels Download PDFInfo
- Publication number
- US2853364A US2853364A US423506A US42350654A US2853364A US 2853364 A US2853364 A US 2853364A US 423506 A US423506 A US 423506A US 42350654 A US42350654 A US 42350654A US 2853364 A US2853364 A US 2853364A
- Authority
- US
- United States
- Prior art keywords
- sodium bisulfate
- stainless steels
- solution
- inhibiting
- corrosiveness
- 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.)
- Expired - Lifetime
Links
- 229910001220 stainless steel Inorganic materials 0.000 title claims description 17
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 title claims description 16
- 229910000342 sodium bisulfate Inorganic materials 0.000 title claims description 16
- 239000007864 aqueous solution Substances 0.000 title claims description 11
- 230000002401 inhibitory effect Effects 0.000 title claims description 10
- 238000000034 method Methods 0.000 title claims description 10
- 239000000243 solution Substances 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 13
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 11
- 238000005260 corrosion Methods 0.000 claims description 8
- 230000007797 corrosion Effects 0.000 claims description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 229910001447 ferric ion Inorganic materials 0.000 description 8
- 230000005764 inhibitory process Effects 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- -1 oxalic acid Chemical class 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical class OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 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 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000003137 locomotive effect Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000000080 wetting agent Substances 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
- C23F11/04—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
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
Definitions
- This invention relates to the corrosion inhibition of an acid salt as regards stainless typesteels, and particularly to a method of inhibiting the corrosiveness in aqueous solution of sodium bisulfate by the incorporation of ferric ion.
- Sodium bisulfate is used in large quantities, either alone or in conjunction with organic acids, such as oxalic acid, for example, as a cleaner for stainless steels, the steel being Washed with an aqueous solution of the salt, or salt and acid mixture, and then the metal rinsed with fresh water.
- organic acids such as oxalic acid
- Sodium bisulfate-containing cleaning compositions are effective in removing grime and other foreign matter from stainless steels but are definitely corrosive to these steels and, furthermore, often cause a black discoloration which is objectionable for esthetic and other reasons.
- Stainless steel equipment is also utilized in chemical manufacture, and it is desirable to inhibit the corrosiveness of sodium bisulfate-containing solutions toward these steels quite part from esthetic considerations.
- the objects of this invention are obtained by incorporating in the salt solution a minor amount of ferric ion by addition to the solution of a ferric salt, preferably a salt of substantial solubility, after which the solution is employed in its customary manner without regard to the fact that the inhibitor is present.
- the inhibited solution may also contain wetting and dispersing agents to facilitate cleaning, where this is the objective, or may contain oxalic acid or one or more of the group consisting of formic, acetic, sulfamic, and glycolic acids either singly or in mixture, the inhibitory effect of ferric ion as regards oxalic acid being taught in my Patent 2,793,190 and as regards formic, acetic, sulfamic, and glycolic acids in my Patent 2,793,191, both filed on the same date as the instant application.
- the following table is a compilation of data covering a number of tests which demonstrate the efiicacy of the method of this invention as regards sodium bisulfate alone in boiling aqueous solution, the ferric ion being intro- .duced by addition of a ferric salt to the solutions, the
- A. I. S. I. 430 and A. I. S. I. 446 are both free of Ni but contain 17% Cr and 25% Cr, respectively.
- the steel analyzing 16% Cr17% Mnl% Ni is representative of the so-called substitute stainless steels, which have recently been utilized extensively in an effort to conserve nickel for national defense purposes, and this invention is also applicable to alloys of this class for which reason the term stainless steels, as used in the appended claims, is intended to comprehend both the conventional and the substitute stainless steels.
- my invention comprises an effective method of inhibiting the corrosiveness of sodium bisulfate in aqueous solution quantity of a ferric ion-contributing salt, but not less than an amount yielding fromabout 0.12 to about 0.65
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Description
tats I Michael'A. Streicher, Wilmington, DeL, assignor to E. I. du Pont de Nemours and Company, Wilmington, DeL, a corporation of Delaware No Drawing. Application April 15, 1954 Serial No. 423,506 a 3 Claims. (Cl. 23-121) This invention relates to the corrosion inhibition of an acid salt as regards stainless typesteels, and particularly to a method of inhibiting the corrosiveness in aqueous solution of sodium bisulfate by the incorporation of ferric ion.
Sodium bisulfate is used in large quantities, either alone or in conjunction with organic acids, such as oxalic acid, for example, as a cleaner for stainless steels, the steel being Washed with an aqueous solution of the salt, or salt and acid mixture, and then the metal rinsed with fresh water. With the advent of stainless steel-sheathed locomotives and railway passenger cars and the growing use of stainless steel fixtures for restaurants, stores and in other merchandising applications, the maintenance of the original bright finish of these alloys has become of widespread concern. Sodium bisulfate-containing cleaning compositions are effective in removing grime and other foreign matter from stainless steels but are definitely corrosive to these steels and, furthermore, often cause a black discoloration which is objectionable for esthetic and other reasons. Stainless steel equipment is also utilized in chemical manufacture, and it is desirable to inhibit the corrosiveness of sodium bisulfate-containing solutions toward these steels quite part from esthetic considerations.
A primary object of this invention is to provide a method of inhibiting the corrosiveness of sodium bisulfate in aqueous solution toward stainless steels. Another object of this invention is to provide a method of inhibiting the corrosiveness of sodium bisulfate in aqueous solution While preventing objectionable contamination of the solutions, and while retaining the original bright surface of the stainless steel intact. Yet another object of this invention is to provide a method of inhibiting the corrosiveness in aqueous solution of sodium bisulfate, with or without one or more of the acids hereinafter mentioned added, for stainless steels which is economical and not dangerous to using personnel.
Generally, the objects of this invention are obtained by incorporating in the salt solution a minor amount of ferric ion by addition to the solution of a ferric salt, preferably a salt of substantial solubility, after which the solution is employed in its customary manner without regard to the fact that the inhibitor is present. The inhibited solution may also contain wetting and dispersing agents to facilitate cleaning, where this is the objective, or may contain oxalic acid or one or more of the group consisting of formic, acetic, sulfamic, and glycolic acids either singly or in mixture, the inhibitory effect of ferric ion as regards oxalic acid being taught in my Patent 2,793,190 and as regards formic, acetic, sulfamic, and glycolic acids in my Patent 2,793,191, both filed on the same date as the instant application.
The following table is a compilation of data covering a number of tests which demonstrate the efiicacy of the method of this invention as regards sodium bisulfate alone in boiling aqueous solution, the ferric ion being intro- .duced by addition of a ferric salt to the solutions, the
2,853,364 Patented Sept. 23, 1958 Uninhib- Minimum ited Oor- Amount of rosion Rate, "Fe Giving g./sq. Complete dm./l1r. Inhibition, g./liter v NaHSOr Concentration in Percent by Weight Steel, AISI Designation Unless Otherwise Indicated It will be understood that A. I. 5.1; 304 steel is the I conventional stainless type containing 18% Cr-8% Ni,
Whereas A. I. S. I. 430 and A. I. S. I. 446 are both free of Ni but contain 17% Cr and 25% Cr, respectively.
The steel analyzing 16% Cr17% Mnl% Ni is representative of the so-called substitute stainless steels, which have recently been utilized extensively in an effort to conserve nickel for national defense purposes, and this invention is also applicable to alloys of this class for which reason the term stainless steels, as used in the appended claims, is intended to comprehend both the conventional and the substitute stainless steels.
It should be mentioned that the quantities of iron reported for attainment of complete inhibition as regards type 304 steel have proved, within 120%, equally effective as regards the A. I. S. I. 300 series steels as a class, including, specifically, 301, 302, 316 and other types.
The tests reported in the table were conducted over periods of 7 hours using boiling sodium bisulfate solutions in the concentrations reported, the concentration level being maintained constant throughout by the use of condensers which returned all material boiled off tothe metal sample-containing flask during the course of the tests. Additional tests, not reported in the table, confirmed the corrosion inhibitory action of ferric ion for much greater periods of time, up to and beyond 60 hours and, independently, for exposures of the steels at lower temperatures. In all of the tests the original bright finish of the steels was preserved intact upon exposure to the corrosion-inhibited salt solutions.
ion into the salt solutions for inhibition purposes, not
only because corrosive halide residues might remain on the metal surfaces, if not removed by thorough rinsing, but also because I have found that the halogen anion exerts an inhibition-counteracting effect on the ferric ion above certain limiting total ferric salt concentration levels. In all cases investigated the ferric salt concentration at which the inhibition-counteracting effect occurred was found to be considerably in excess of the ferric ion concentration which it was necessary to maintain for complete corrosion inhibition, and therefore halogen salts are effective for the purposes of this invention, with the limitations mentioned.
All of the data hereinbefore set out is convertible to the basis of penetration in inches per month by simply multiplying by the factor 0.36.
The mechanism responsible for the corrosion inhibition of sodium bisulfatecontaining aqueous solutions toward stainless steels, while keeping the surface bright, is not understood; however, the effect appears to result from a specific property of the ferric ion itself.
From the foregoing it will be understood that my invention comprises an effective method of inhibiting the corrosiveness of sodium bisulfate in aqueous solution quantity of a ferric ion-contributing salt, but not less than an amount yielding fromabout 0.12 to about 0.65
gram/ liter of said solution of ferric iron, depending uponthe concentration of sodium bisulfate in said solution and the steel involved, and thereafter contacting said stainless steels with said solution.
2. The method according to claim 1 in which said ferric ion-contributing salt is free of halogen.
3. The method of, substantially inhibiting the corrosion of sodium bisulfate in aqueous solution toward stainless steels comprising incorporating in said solution a minor quantity of a ferric ion-contributing salt furnishing a minimum ranging fromabout 0.12 to about 0.65 gram/ liter of said solution of ferric iron, depending upon the concentration of sodium bisulfate in the solution and the steel involved, but less than the corrosion inhibitioncounteracting equivalent of the anion of said salt, and thereafter contacting said stainless steels with said solution.
References Cited in the file of this patent UNITED STATES PATENTS 1,599,996 Fritz Sept. 14, 1926 2,238,651 Keenen Apr. 25, 1941 2,666,209 Sherva Jan. 19, 1954 2,761,765 Matthews Sept. 1956 FOREIGN PATENTS 632,533 Great Britain Nov. 28, 1949
Claims (1)
1. THE METHOD OF SUBSTANTIALLY INHIBITING THE CORROSION OF SODIUM BISULFATE IN AQUEOUS SOLUTION TOWARD STAINLESS STEELS COMPRISING INCORPORATING IN SAID SOLUTION A MINOR QUANTITY OF A FERRIC ION-CONTRIBUTNG SALT, BUT NOT LESS THAN AN AMOUNT YIELDING FROM ABOUT 0.12 TO ABOUT 0.65 GRAM/LITER FO SAID SOLUTION OF FERRIC IRON, DEPENDING UPON THE CONCENTRATION OF SODIUM BISULFATE IN SAID SOLUTION AND THE STEEL INVOLVED, AND THEREAFTER CONTACTING SAID STAINLESS STEELS WITH SOLUTION.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US423506A US2853364A (en) | 1954-04-15 | 1954-04-15 | Method of inhibiting the corrosiveness of aqueous solutions of sodium bisulfate towards stainless steels |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US423506A US2853364A (en) | 1954-04-15 | 1954-04-15 | Method of inhibiting the corrosiveness of aqueous solutions of sodium bisulfate towards stainless steels |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2853364A true US2853364A (en) | 1958-09-23 |
Family
ID=23679138
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US423506A Expired - Lifetime US2853364A (en) | 1954-04-15 | 1954-04-15 | Method of inhibiting the corrosiveness of aqueous solutions of sodium bisulfate towards stainless steels |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2853364A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1599996A (en) * | 1926-09-14 | Cleaning compound and process of preventing the deliquescence of a salt | ||
| US2238651A (en) * | 1937-05-21 | 1941-04-15 | Du Pont | Inhibition of corrosion |
| GB632533A (en) * | 1946-07-22 | 1949-11-28 | Ici Ltd | Improvements in or relating to corrosion inhibition |
| US2666209A (en) * | 1951-12-24 | 1954-01-19 | Sherva Clara | Patient's urinal |
| US2761765A (en) * | 1952-10-28 | 1956-09-04 | Pure Oil Co | Composition and method of inhibiting the corrosion of ferrous equipment used in the regeneration and boiling of alkali metal solutions |
-
1954
- 1954-04-15 US US423506A patent/US2853364A/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1599996A (en) * | 1926-09-14 | Cleaning compound and process of preventing the deliquescence of a salt | ||
| US2238651A (en) * | 1937-05-21 | 1941-04-15 | Du Pont | Inhibition of corrosion |
| GB632533A (en) * | 1946-07-22 | 1949-11-28 | Ici Ltd | Improvements in or relating to corrosion inhibition |
| US2666209A (en) * | 1951-12-24 | 1954-01-19 | Sherva Clara | Patient's urinal |
| US2761765A (en) * | 1952-10-28 | 1956-09-04 | Pure Oil Co | Composition and method of inhibiting the corrosion of ferrous equipment used in the regeneration and boiling of alkali metal solutions |
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