US2470428A - Suppression of corrosive action of carbonic acid - Google Patents

Suppression of corrosive action of carbonic acid Download PDF

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Publication number
US2470428A
US2470428A US626447A US62644745A US2470428A US 2470428 A US2470428 A US 2470428A US 626447 A US626447 A US 626447A US 62644745 A US62644745 A US 62644745A US 2470428 A US2470428 A US 2470428A
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Prior art keywords
carbon dioxide
carbonic acid
suppression
corrosive action
corrosion
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Expired - Lifetime
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US626447A
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Elza Q Camp
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Standard Oil Development Co
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Standard Oil Development Co
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Priority to US626447A priority Critical patent/US2470428A/en
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-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
    • C23F11/00Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10Inhibiting 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 organic inhibitors
    • C23F11/16Sulfur-containing compounds

Definitions

  • This invention is directed to a method for suppressing the corrosion of ferrous metals in the presence of carbonic acid. Specifically, it is directed to the prevention of corrosion of steel in water containing dissolved carbon dioxide.
  • the afore-mentioned corrosion reaction occurs at atmospheric temperature and pressure. Higher temperatures and pressures accelerate this type of reaction.
  • the main object of the present invention to provide a process whereby the corrosion of steel equipment in the presence of water solutions of carbon dioxide is substantially eliminated.
  • corrosion resulting from the afore-mentioned type of reactions involving carbonic acid solutions is substantially eliminated by including in the water solutions of carbon dioxide small amounts of sulfur compounds, which may be termed non-metal sulfides and may be illustrated by hydrogen sulfide, aliphatic mercaptans such as butyl mer captan, and inorganic and organic sulfides such as ammonium hydrosulfide, carbon disulfide, and the like.
  • sulfur compounds which may be termed non-metal sulfides and may be illustrated by hydrogen sulfide, aliphatic mercaptans such as butyl mer captan, and inorganic and organic sulfides such as ammonium hydrosulfide, carbon disulfide, and the like.
  • An advantage of the process of the present invention is the ability to use existing equipment in which ferrous metals are present in processes involving the use of water in which is dissolved carbon dioxide.
  • carbon steel was immersed in air saturated distilled water under a pressure of 35 pounds per square inch gage of carbon dioxide. The tests were in progress for 24 hours at a temperature of F. The carbon dioxide was admitted to the system through a pressure regulator valve, thus maintaining a constant pressure of 35 pounds per square inch gage on the system and thereby maintainin the distilled water in which the carbon steel was immersed saturated with carbon dioxide at the temperature and pressure at which the tests were conducted. The carbon steel was weighed carefully prior to immersing in the aqueous solution of carbon dioxide and after the period of exposure to the solution the steel was removed from the solution, corrosion products cleaned away and the steel was reweighed. Loss in weight was calculated on the basis of penetration in inches per year since this is the common way of reporting corrosion of metals by corrosive solutions. The results obtained in these tests are shown in the following table:
  • a method of reducing the corrosive action of a mixture consisting of water, air and carbon dioxide in contact with ferrous metal in steam boiler systems which comprises injecting in said system an inhibiting amount of carbon disulfide.
  • a method of reducing the corrosive action of a mixture consisting of water, air, and carbon dioxide in contact with ferrous metals which comprises maintaining in said mixture an inhibiting amount of carbon disulfide in the range between 0.1 and 2.0% by weight of the mixture.

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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

Patented May 17, 1949 SUPPRESSION OF CORROSIVE ACTION OF CARBONIC ACID Elza Q. Camp, Goose Creek, Tex, assignor to Standard Oil Development Company, a corporation of Delaware No Drawing. Application November 2, 1945, Serial No. 626,447
2 Claims. 1
This invention is directed to a method for suppressing the corrosion of ferrous metals in the presence of carbonic acid. Specifically, it is directed to the prevention of corrosion of steel in water containing dissolved carbon dioxide.
In many operations, it is desirable to use steel equipment (valves, lines, exchanger shells, tube bundles, etc.) in the presence of water containin dissolved carbon dioxide. More specifically, it is desirable to use steel equipment in the presence of steam condensate in which is dissolved carbon dioxide and small amounts of oxygen. It is commonly known that water solutions of carbon dioxide are corrosive to steel equipment.
The afore-mentioned corrosion reaction occurs at atmospheric temperature and pressure. Higher temperatures and pressures accelerate this type of reaction.
It is, therefore, the main object of the present invention to provide a process whereby the corrosion of steel equipment in the presence of water solutions of carbon dioxide is substantially eliminated.
In accordance with the present invention, corrosion resulting from the afore-mentioned type of reactions involving carbonic acid solutions is substantially eliminated by including in the water solutions of carbon dioxide small amounts of sulfur compounds, which may be termed non-metal sulfides and may be illustrated by hydrogen sulfide, aliphatic mercaptans such as butyl mer captan, and inorganic and organic sulfides such as ammonium hydrosulfide, carbon disulfide, and the like.
The amounts of these materials employed to prevent the afore-mentioned types of corrosion reaction are small and will vary with the individual sulfur compounds. Illustrative concentrations are as follows:
Weight Per Cent, Based on Water Material Added Solution of Cab The mechanism by which these materials are effective in preventing corrosion is not understood, but it is believed to be due to the formation of a protective film on the metal. It is understood, of course, that I do not wish to bind myself to any theory offered as explanation of the beneficial effect.
An advantage of the process of the present invention, irrespective of the prevention of corrosion of ferrous metals, is the ability to use existing equipment in which ferrous metals are present in processes involving the use of water in which is dissolved carbon dioxide.
In order to illustrate the beneficial effects of this invention, carbon steel was immersed in air saturated distilled water under a pressure of 35 pounds per square inch gage of carbon dioxide. The tests were in progress for 24 hours at a temperature of F. The carbon dioxide was admitted to the system through a pressure regulator valve, thus maintaining a constant pressure of 35 pounds per square inch gage on the system and thereby maintainin the distilled water in which the carbon steel was immersed saturated with carbon dioxide at the temperature and pressure at which the tests were conducted. The carbon steel was weighed carefully prior to immersing in the aqueous solution of carbon dioxide and after the period of exposure to the solution the steel was removed from the solution, corrosion products cleaned away and the steel was reweighed. Loss in weight was calculated on the basis of penetration in inches per year since this is the common way of reporting corrosion of metals by corrosive solutions. The results obtained in these tests are shown in the following table:
It will be observed from the data presented in 0 the foregoing table that the addition of small amounts of either carbon disulfide, butyl mercaptan, ammonium hydrosulfide, or hydrogen sulfide effects marked reductions in the tendency of water solutions of carbon dioxide to corrode steel.
The nature and objects of the present invention having been fully described and illustrated, what I wish to claim as new and useful and to secure by Letters Patent is:
1. A method of reducing the corrosive action of a mixture consisting of water, air and carbon dioxide in contact with ferrous metal in steam boiler systems which comprises injecting in said system an inhibiting amount of carbon disulfide.
2. A method of reducing the corrosive action of a mixture consisting of water, air, and carbon dioxide in contact with ferrous metals which comprises maintaining in said mixture an inhibiting amount of carbon disulfide in the range between 0.1 and 2.0% by weight of the mixture.
ELZA Q. CAMP.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 2,075,976 Calcott Apr. 6, 1937 FOREIGN PATENTS Number Country Date 314,842 Great Britain July 11, 1929 OTHER REFERENCES
US626447A 1945-11-02 1945-11-02 Suppression of corrosive action of carbonic acid Expired - Lifetime US2470428A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3062612A (en) * 1959-04-25 1962-11-06 Inst Francais Du Petrole Method of protecting metals against electrochemical corrosion of the acidic type
WO2000008235A1 (en) * 1998-08-07 2000-02-17 Hahn-Meitner-Institut Berlin Gmbh Use of di-tert-butylsulphide (tbds) and/or tert-butylmercaptan (tbm) as corrosion inhibitors in microbial corrosion of metals

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB314842A (en) * 1928-04-11 1929-07-11 Kenneth Gordon Improvements in the regeneration of washing liquids employed in removing carbon dioxide and other soluble constituents from gases
US2075976A (en) * 1933-09-07 1937-04-06 Du Pont Prevention of corrosion

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB314842A (en) * 1928-04-11 1929-07-11 Kenneth Gordon Improvements in the regeneration of washing liquids employed in removing carbon dioxide and other soluble constituents from gases
US2075976A (en) * 1933-09-07 1937-04-06 Du Pont Prevention of corrosion

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3062612A (en) * 1959-04-25 1962-11-06 Inst Francais Du Petrole Method of protecting metals against electrochemical corrosion of the acidic type
WO2000008235A1 (en) * 1998-08-07 2000-02-17 Hahn-Meitner-Institut Berlin Gmbh Use of di-tert-butylsulphide (tbds) and/or tert-butylmercaptan (tbm) as corrosion inhibitors in microbial corrosion of metals

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