US2550434A - Suppression of corrosion - Google Patents
Suppression of corrosion Download PDFInfo
- Publication number
- US2550434A US2550434A US602860A US60286045A US2550434A US 2550434 A US2550434 A US 2550434A US 602860 A US602860 A US 602860A US 60286045 A US60286045 A US 60286045A US 2550434 A US2550434 A US 2550434A
- Authority
- US
- United States
- Prior art keywords
- corrosion
- solution
- amount
- alkaline
- copper
- 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
- 238000005260 corrosion Methods 0.000 title description 21
- 230000007797 corrosion Effects 0.000 title description 21
- 230000001629 suppression Effects 0.000 title description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 239000010949 copper Substances 0.000 claims description 14
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 9
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 8
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- 230000002401 inhibitory effect Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000000243 solution Substances 0.000 description 16
- 150000001875 compounds Chemical class 0.000 description 13
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 12
- 230000002378 acidificating effect Effects 0.000 description 10
- 239000012530 fluid Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 8
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 7
- 229940012189 methyl orange Drugs 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000001996 bearing alloy Substances 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 241000272814 Anser sp. Species 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical class CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 description 1
- 230000003292 diminished effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000011005 laboratory method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
Images
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
- C23F11/06—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly alkaline liquids
Definitions
- the present invention is directed to a method 'for suppressing the corrosion of a surface comprising a major portion of metallic copper which is exposed to a fluid comprising an alkaline com pound in corrosion-producing amounts.
- the fluid becomes contaminated by acid which causes the relatively rapid corrosion of parts, constructed, for example, of steel, used in fabricating a relatively large portion of the equipment used. It is desirable to add an alkaline reagent to the fluid being passed through the apparatus in order to reduce the acidity of the fluid and render it less corrosive to these parts.
- the equipment employed in handling the fluid is usually not manufactured of a single metal or metallic alloy but instead includes several dissimilar metals.
- the walls of vessels and the piping connecting vessels may be constructed of steel, it is common to employ copper or copper alloys in conjunction therewith; in heat exchangers and condensers the shells may be of steel and the tubes of copper or a copper-bearing alloy such as Admiralty metals.
- the addition of an alkaline agent to the acid-containing fluid being processed may reduce or eliminate the corrosion of that part of the apparatus constructed of ferrous materials, the contact of the alkaline reagent with the copper or copper-bearing alloys may cause corrosion of these parts at a relatively rapid rate.
- the corrosion of a surface comprising a major portion of metallic copper when brought into contact with an aqueous solution including an alkaline reagent in corrosion-producing amounts is suppressed by the addition to the solution of an acidic sulfur-containing compound.
- the acidic sulfur-containing compound should be added in an amount in excess of a predetermined minimum.
- the predetermined minimum amount of acidic sulfur-containing compound may be expressed either in terms of the molar ratio of acid reacting sulfur compounds to alkaline reagents in the solution or in terms of the ratio of the phenolphthalein end point to the methyl orange end point.
- acidic sulfur-containing compounds suitable for use as the inhibiting agent in the practice of the present invention may be mentioned hydrogen sulfide, sulfur dioxide and mercaptans, such as ethyl, propyl and butyl mercaptans. It will be understood that these specific compounds are given by way of example only and for the purpose of illustrating generally the class of acidic sulfurcontaining compounds to be used in the present invention.
- a method of inhibiting the corrosiveness of a corrosive solution consisting of an alkali metal hydroxide and water in contact with a corrodible copper surface which consists in the step of maintaining in said corrosive solution While in contact with said corrodible copper surface an amount 7 of combined hydrogen sulfide in an amount at least 0.1 mole per mole of alkali metal hydroxide and less than required to neutralize all the alkali metal hydroxide.
- a method of inhibiting the corrosiveness of a corrosive solution consistingof sodium hydroxide and water having a gravity of 4 degrees Baum in contact with a corrodible copper surface which consists in the step of maintaining in said corrosive solution while in contact with said corrodible copper surface an amount of combined hydrogen sulfide in an amount at least 0.1 mole per mole of sodium hydroxide and less than required to neutralize all the sodium hydroxide.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Description
April 1951 P. s. VILES EI'AL SUPPRESSION 0F CORROSION Filed July 2, 1945 Sodium Hydroxide Solution Plus Hydrogen Sulfide 6 5 4 3 o o O O O O .035. o Eu :0 ti: w um commotoo Moles Hydrogen Sulfide Per Mole of Sodium Hydroxide INV 101:3. I fi/zmzizgf Mia M Patented Apr. 24, 1951 um'reo sr T E S SUPPRESSION F CORROSION Prentiss S. Viles and David C. Walsh, Jr., Goose Creek, Tex., assignors to Standard Oil Development Company,
a corporation of Delaware 3 Claims.
The present invention is directed to a method 'for suppressing the corrosion of a surface comprising a major portion of metallic copper which is exposed to a fluid comprising an alkaline com pound in corrosion-producing amounts.
In many commercial operations involving the prdcessing of fluid components, the fluid becomes contaminated by acid which causes the relatively rapid corrosion of parts, constructed, for example, of steel, used in fabricating a relatively large portion of the equipment used. It is desirable to add an alkaline reagent to the fluid being passed through the apparatus in order to reduce the acidity of the fluid and render it less corrosive to these parts. However, the equipment employed in handling the fluid is usually not manufactured of a single metal or metallic alloy but instead includes several dissimilar metals. For example, while the walls of vessels and the piping connecting vessels may be constructed of steel, it is common to employ copper or copper alloys in conjunction therewith; in heat exchangers and condensers the shells may be of steel and the tubes of copper or a copper-bearing alloy such as Admiralty metals. While the addition of an alkaline agent to the acid-containing fluid being processed may reduce or eliminate the corrosion of that part of the apparatus constructed of ferrous materials, the contact of the alkaline reagent with the copper or copper-bearing alloys may cause corrosion of these parts at a relatively rapid rate.
It is an object of the present invention to suppress the corrosion of a surface comprising a major portion of metallic copper which is contacted with a fluid in which an alkaline compound is present in corrosion-producing amounts.
In accordance with the present invention the corrosion of a surface comprising a major portion of metallic copper when brought into contact with an aqueous solution including an alkaline reagent in corrosion-producing amounts is suppressed by the addition to the solution of an acidic sulfur-containing compound. For the most satisfactory results in suppressing the corrosion, the acidic sulfur-containing compound should be added in an amount in excess of a predetermined minimum. The predetermined minimum amount of acidic sulfur-containing compound may be expressed either in terms of the molar ratio of acid reacting sulfur compounds to alkaline reagents in the solution or in terms of the ratio of the phenolphthalein end point to the methyl orange end point. When expressing the amount of acidic sulfur-containing compound in the alkaline fluid in terms of molar ratio, it may be stated that for the most satisfactory results it is desirable for the solution to have added to it no less than 0.1 mole of acidic sulfurcontaining compound for every mole of alkaline reagent present in the solution. When expressing the amount of acidic sulfur-containing compound added to the alkaline solution in terms of phenolphthalein end point and methyl orange end point, it may be stated that upon the titration of a given amount of the solution with. a standardized acid solution employing phenolphth'alein as the indicator and carrying out the titration under the same conditions but employing methyl orange as the indicator, the ratio of twice the amount of standardized acid solution employed using phenolphthalein to the amount of standardized acid solution employed when using methyl orange as the indicator should be no less than 1.8. As specific examples of acidic sulfur-containing compounds suitable for use as the inhibiting agent in the practice of the present invention may be mentioned hydrogen sulfide, sulfur dioxide and mercaptans, such as ethyl, propyl and butyl mercaptans. It will be understood that these specific compounds are given by way of example only and for the purpose of illustrating generally the class of acidic sulfurcontaining compounds to be used in the present invention.
The practice of the present invention will now be described in further detail by the following example:
EXAMPLE A 4 B. aqueous sodium hydroxide solution was divided into five equal portions. One portion was retained in its original state and hydrogen sulfide was added to the remaining portion such that the molar ratio of H28 to NaOH was 0.098, 0.5, 0.6 and 0.77 in the respective samples. The corrosion rate of Admiralty metal in each of the samples was then determined in accordance with usual laboratory methods for determining rate of corrosion. The characteristics of the samples, both as to the molar ratio of HzS and NaOH and the ratio of twice the phenolphthalein end point to the methyl orange end point as well as the corrosion rate are given in the following table:
Table Corrosion Rate in./yr. Penetration Admiralty Metal... 0 0 0.011 0. 004 0.002 0.004
2 X (Phenolphthalein end point Methyl Orange End Point... 2.0 1.795 1.0 0.805 0. 42 pH 11.8 11.8 11.8 11.7 Moles ms bsorbed in Each Mole ofNaOH 0. 098 0.5 0.6 0.77
It will be seen from the above table that when the acidic sulfur-containing compound is added to the solution containing an alkaline reagent in such amounts as to adjust the molar ratio of the acidic sulfur-containing compound to the alkaline agent within the range of 0.1 to 1, the corrosion rate of the solution is markedly diminished. When the amount of acidic-sulfur containing compound in the alkaline solution is expressed in ratio of twice the phenolphthalein end point to methyl orange end point it will be seen that when the ratio is 1.8 or less the rate of corrosion is greatly reduced over the rate of corrosion of the original alkaline solution.
The results obtained in the example are shown in the drawing which is in the form of a curve in which the corrosion rate of the Admiralty metal is plotted as the abscissa and the ratio of moles of hydrogen sulfide per mole of sodium hydroxide is plotted as the ordinate. The tests carried out on the samples as set out in the table are shown onthe" drawing as small circles which appear on or adjacent the curve.
Having fully described and illustrated the practice'of the present invention, what is desired to be claimed as new and useful and secured by Letters Patent is:
1. A method of inhibiting the corrosiveness of a corrosive solution consisting of an alkali metal hydroxide and water in contact with a corrodible copper surface which consists in the step of maintaining in said corrosive solution While in contact with said corrodible copper surface an amount 7 of combined hydrogen sulfide in an amount at least 0.1 mole per mole of alkali metal hydroxide and less than required to neutralize all the alkali metal hydroxide.
2. A method in accordance with claim 1 in which the alkali metal hydroxide is sodium hydroxide.
3. A method of inhibiting the corrosiveness of a corrosive solution consistingof sodium hydroxide and water having a gravity of 4 degrees Baum in contact with a corrodible copper surface which consists in the step of maintaining in said corrosive solution while in contact with said corrodible copper surface an amount of combined hydrogen sulfide in an amount at least 0.1 mole per mole of sodium hydroxide and less than required to neutralize all the sodium hydroxide.
PRENTISS S. VILES. DAVID C. WALSH, JR.
REFERENCES CITED UNITED STATES PATENTS Number Name 'Date 223,814 Pennington Jan. 27, 1880 1,949,781 Champlin ans, 1934 2,054,282 Clarkson Sept. 15, 193 6 2,238,651 Keenen Apr. 15, 1941 2,385,175 Wachter Sept. 18, 1945 2,426;08'7 Fetterly Aug. 19, 1947 2,432,301 Fetterly Dec. 9, 1947 FOREIGN PATENTS Number Country Date 488,972 Great Britain July 18, 1938
Claims (1)
1. A METHOD OF INHIBITING THE CORROSIVENESS OF A CORROSIVE SOLUTION CONSISTING OF AN ALKALI METAL HYDROXIDE AND WATER IN CONTACT WITH A CORRODIBLE COPPER SURFACE WHICH CONSISTS IN THE STEP OF MAINTAINING IN SAID CORROSIVE SOLUTION WHILE IN CONTACT WITH SAID CORRODIBLE COPPER SURFACE AN AMOUNT OF COMBINED HYDROGEN SULFIDE IN AN AMOUNT AT LEAST 0.1 MOLE PER MOLE OF ALKALI METAL HYDROXIDE AND LESS THAN REQUIRED TO NEUTRALIZED ALL THE ALKALI METAL HYDROXIDE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US602860A US2550434A (en) | 1945-07-02 | 1945-07-02 | Suppression of corrosion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US602860A US2550434A (en) | 1945-07-02 | 1945-07-02 | Suppression of corrosion |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2550434A true US2550434A (en) | 1951-04-24 |
Family
ID=24413079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US602860A Expired - Lifetime US2550434A (en) | 1945-07-02 | 1945-07-02 | Suppression of corrosion |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2550434A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3282848A (en) * | 1964-01-28 | 1966-11-01 | Du Pont | Process and composition for the removal of tarnish on metals |
| US3345295A (en) * | 1963-02-13 | 1967-10-03 | Shulton Inc | Copper cleaning compositions |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US223814A (en) * | 1880-01-27 | Preparing paper and other fabrics and materials for wrapping silver and other metals | ||
| US1949781A (en) * | 1933-03-08 | 1934-03-06 | Arthur D Champlin | Tarnishproof cloth |
| US2054282A (en) * | 1935-04-11 | 1936-09-15 | Du Pont | Noncorrosive aqueous solutions |
| GB488972A (en) * | 1937-01-13 | 1938-07-18 | Paasch & Larsen Petersen As | Process for cleaning of pasteurizing apparatuses consisting wholly or partly of rustless steel |
| US2238651A (en) * | 1937-05-21 | 1941-04-15 | Du Pont | Inhibition of corrosion |
| US2385175A (en) * | 1943-10-13 | 1945-09-18 | Shell Dev | Pipe-line corrosion inhibition |
| US2426087A (en) * | 1944-06-26 | 1947-08-19 | Shell Dev | Conversion of hydrosulfides to neutral sulfur substances |
| US2432301A (en) * | 1944-06-26 | 1947-12-09 | Shell Dev | Conversion of hydrosulfides to neutral sulfur compounds |
-
1945
- 1945-07-02 US US602860A patent/US2550434A/en not_active Expired - Lifetime
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US223814A (en) * | 1880-01-27 | Preparing paper and other fabrics and materials for wrapping silver and other metals | ||
| US1949781A (en) * | 1933-03-08 | 1934-03-06 | Arthur D Champlin | Tarnishproof cloth |
| US2054282A (en) * | 1935-04-11 | 1936-09-15 | Du Pont | Noncorrosive aqueous solutions |
| GB488972A (en) * | 1937-01-13 | 1938-07-18 | Paasch & Larsen Petersen As | Process for cleaning of pasteurizing apparatuses consisting wholly or partly of rustless steel |
| US2238651A (en) * | 1937-05-21 | 1941-04-15 | Du Pont | Inhibition of corrosion |
| US2385175A (en) * | 1943-10-13 | 1945-09-18 | Shell Dev | Pipe-line corrosion inhibition |
| US2426087A (en) * | 1944-06-26 | 1947-08-19 | Shell Dev | Conversion of hydrosulfides to neutral sulfur substances |
| US2432301A (en) * | 1944-06-26 | 1947-12-09 | Shell Dev | Conversion of hydrosulfides to neutral sulfur compounds |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3345295A (en) * | 1963-02-13 | 1967-10-03 | Shulton Inc | Copper cleaning compositions |
| US3282848A (en) * | 1964-01-28 | 1966-11-01 | Du Pont | Process and composition for the removal of tarnish on metals |
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