US1992689A - Corrosion inhibitor - Google Patents

Corrosion inhibitor Download PDF

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Publication number
US1992689A
US1992689A US495302A US49530230A US1992689A US 1992689 A US1992689 A US 1992689A US 495302 A US495302 A US 495302A US 49530230 A US49530230 A US 49530230A US 1992689 A US1992689 A US 1992689A
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United States
Prior art keywords
corrosion
hydroxy
acid
liquid
triethanolamine
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Expired - Lifetime
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US495302A
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Henry L Cox
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Carbide and Carbon Chemicals Corp
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Carbide and Carbon Chemicals Corp
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Priority to US495302A priority Critical patent/US1992689A/en
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08—Materials not undergoing a change of physical state when used
    • 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
    • C23F11/10—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 organic inhibitors
    • 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
    • C23F11/10—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 organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds
    • C23F11/143—Salts of amines

Definitions

  • This invention relates to the prevention of metal corrosion. induced by the presence of certain liquids.
  • the invention is especially applicable to coolingsystems which are constructed combustion engines which employ water, alcohols, or water solutions of alcohols for the circulating liquid, but it may be applied to other liquid systems which are subject to corrosion.
  • alcohols in solution with water are used in the cooling systems of internal combustion engines, and in certain instances alcohols alone may beused for this purpose. My invention is especially applicable to prevent the oxi-' dizing action of such cooling media.
  • the term alcohol as used in. this specification and the appended claims includes all the liquid saturated aliphatic hydroxy compounds.
  • the compounds of this class which have been used extensively are the mono-hydroxy alcohols, such as metha nol, ethanol, propanol, and the poly-hydroxy alcohols such as ethylene glycol, diethylene glycol, propylene glycol and glycerol.
  • Corrosion of the metallic parts of liquid systems commonly results in a lowered efliciency of the system. Corrosion roughens the heating and cooling surfaces, and produces sediment and sludge which impair the heat transferring functions of the systems. Excessive corrosion causes-leaking which necessitates repair or replacement of the damaged parts.
  • substantially non-corrosive liquids such as pure water, is impracticable since it is usually impossible to prevent contamination of the liquids by adventitious additions of gases, and other corrosion producing substances to which the liquids are exposed. It is furthermore desirable that the non-corrosive liquid employed should be stable, free from disagreeable odors, and free from objectionable color or stain producing properties.
  • One of the objects of my invention is to provide means for rendering and maintaining liquid media substantially non-corrosive to metals.
  • Another object of my invention is to provide an apparatus for the dissipation of heat in which the metal portions shall be substantially free from corrosion.
  • Cooling media containing additions of a hydroxy-alkylamine have been found satisfactory in inhibiting corrosion in respect to iron and certain related metals and alloys. However, such additions may render the media unduly corrosive toward metals and alloys which are attacked under alkaline conditions. I have found that this difliculty may be avoided by partially or wholly neutralizing the hydroxy-alkylamine by means of an acid.
  • the acid used may be an inorganic acid such as phosphoric acid, or .an organic acid such as oleic, palmitic or stearic acid. It may be added as such, or in the case of the organic acid, it may be supplied in the form of lard oil or similar glycerides containing free fatty acids.
  • a cooling system composed mainly of iron was operated with water in which 0.25% by weight of triethanolamine was dissolved.
  • the corrosion produced in this system was found to be only about seven ,thousandths as much as that produced by water alone, under the same conditions of operation.
  • a cooling system composed mainly of iron, 25 was operated with water in which 1.0 by weight of triethanolamine phosphate was dissolved. In this casethe corrosion produced was too slight to be determinedJThis composition was found to be nearly equally advantageous when used in cooling systems comprisingother metals and alloys, namely, brass, copper and solder.
  • Example III A cooling system'composed mainly of iron was operated with water to which was added 0.25% by weight of triethanolamine partially neutralized with 0.5% by weight of lard oil containing about 10% 15% free fatty acid.- As in Example II, this composition was used in systems composed of other metals, and in all cases reduced corrosion to negligible proportions.
  • Cooling systems like those described in Example II were operated with an alcohol as the cooling medium, with about 0.33% by weight of triethanolamine in the alcohol; with about 1.5% by weight of triethanolamine phosphate in the 55 alcohol; and with about 0.75% by weight of triethanolamine neutralized in part with about 1.5%
  • Mono or diethanolamine, mixtures of mono-, diand triethanolamine, or other hydroxy-alkylamines, such as propanolamine, etc., may be used instead of triethanolamine.
  • Salts of inorganic and organic acids, such as the borates, acetates, formates and oxalates of hydroxy-alkylamines may be used instead of the phosphate, or the hydroxy-alkylamine may be partially or wholly neutralized with a fatty acid, such as stearic acid, oleic acid, palmitic acid, or mixtures of fatty acids, such as those found in lard oil and similar organic oils.
  • the result of the added inhibitor is to produce and maintain conditions in the solution which will render the liquid less corroslve to metal. Since an acidic condition is, in the main, the most prevalent in untreated liquids that are corrosive, the inhibitor added is in each case alkaline.
  • the hydroxy-alkylamine whenused alone neutralizes the undesirable acidity, but as has been stated, excessive alkalinity is undesirable, and somewhat more beneficial results are produced by partially neutralizing the alkaline hydroxy-alkylamine with an acid. It is necessary to use an acid which will form stable salts with the hydroxy-alkylamine, such salts being inert in respect to the liquid used, and producing a wholly stable condition in the final solution.
  • hydroxy-alkylamine is to be neutralized or partly neutralized by-means of lard oil or similar glycerides, excess amounts may be used inasmuch as the presence of the oil or the glycerides will not cause injurious corrosion in the system.
  • the concentration of the inhibitor in the liquid is dependent upon the liquid to be treated, the inhibitor to be used and the metals of which the liquid system is formed.
  • the limits of concentration may, however, be determined by well knowntests. Thus, it has been determined that in a 35% solution by volume of ethylene glycol in water, the most satisfactory limits of concentration which will produce non-corrosive solutions are as follows:
  • a liquid cooling medium for use in conjunction with a metal radiator comprising an alcohol and a salt of an acid of the group consisting of oleic, palmitic and stearic and an ethanolamine,
  • said salt being present in suflicient quantity to inhibit the corrosion of said radiator.

Description

of metals, such as the cooling systems of internal Patented Feb. 26, 1935 UNITED STATE CORROSION INHIBITOR Henry L. Cox, Charleston, W. Va., aaaignor to .Carbide and Carbon Chemicals Corporation, a
corporation .of New York No Drawing.
Application November Serial No. 495,302
3 Claims. (01. zsz---s) This invention relates to the prevention of metal corrosion. induced by the presence of certain liquids. The invention is especially applicable to coolingsystems which are constructed combustion engines which employ water, alcohols, or water solutions of alcohols for the circulating liquid, but it may be applied to other liquid systems which are subject to corrosion.
Various alcohols in solution with water are used in the cooling systems of internal combustion engines, and in certain instances alcohols alone may beused for this purpose. My invention is especially applicable to prevent the oxi-' dizing action of such cooling media. The term alcohol as used in. this specification and the appended claims, includes all the liquid saturated aliphatic hydroxy compounds. The compounds of this class which have been used extensively are the mono-hydroxy alcohols, such as metha nol, ethanol, propanol, and the poly-hydroxy alcohols such as ethylene glycol, diethylene glycol, propylene glycol and glycerol.
Corrosion of the metallic parts of liquid systems, such as those portions comprising iron, copper, brass or solder, commonly results in a lowered efliciency of the system. Corrosion roughens the heating and cooling surfaces, and produces sediment and sludge which impair the heat transferring functions of the systems. Excessive corrosion causes-leaking which necessitates repair or replacement of the damaged parts. The use of substantially non-corrosive liquids, such as pure water, is impracticable since it is usually impossible to prevent contamination of the liquids by adventitious additions of gases, and other corrosion producing substances to which the liquids are exposed. It is furthermore desirable that the non-corrosive liquid employed should be stable, free from disagreeable odors, and free from objectionable color or stain producing properties.
One of the objects of my invention is to provide means for rendering and maintaining liquid media substantially non-corrosive to metals.
Another object of my invention is to provide an apparatus for the dissipation of heat in which the metal portions shall be substantially free from corrosion.
Cooling media containing additions of a hydroxy-alkylamine, such as triethanolamine, have been found satisfactory in inhibiting corrosion in respect to iron and certain related metals and alloys. However, such additions may render the media unduly corrosive toward metals and alloys which are attacked under alkaline conditions. I have found that this difliculty may be avoided by partially or wholly neutralizing the hydroxy-alkylamine by means of an acid. The acid used may be an inorganic acid such as phosphoric acid, or .an organic acid such as oleic, palmitic or stearic acid. It may be added as such, or in the case of the organic acid, it may be supplied in the form of lard oil or similar glycerides containing free fatty acids.
These salts of hydroxy-alkylamines either with or without the presence of the free bydroxy-alkylamine, have been found to be very eillcient as inhibitors of corrosion in liquid systems.
The following examples are illustrative of my invention: 1
I. A cooling system composed mainly of iron was operated with water in which 0.25% by weight of triethanolamine was dissolved. The corrosion produced in this system was found to be only about seven ,thousandths as much as that produced by water alone, under the same conditions of operation.
. II. A cooling system composed mainly of iron, 25 was operated with water in which 1.0 by weight of triethanolamine phosphate was dissolved. In this casethe corrosion produced was too slight to be determinedJThis composition was found to be nearly equally advantageous when used in cooling systems comprisingother metals and alloys, namely, brass, copper and solder.
III. A cooling system'composed mainly of iron was operated with water to which was added 0.25% by weight of triethanolamine partially neutralized with 0.5% by weight of lard oil containing about 10% 15% free fatty acid.- As in Example II, this composition was used in systems composed of other metals, and in all cases reduced corrosion to negligible proportions.
IV. Cooling, systems like those described in Example 11 were operated with a water solution of an alcohol containing 1.0% by weight of triethanolamine phosphate. The corrosion produced wasnegligible as compared to that produced by a solution containing only water and alcohol.
An alcohol solution containing 0.25% by weight of triethanolamine, and 0.5% by weight of lard oil gave 'very similar results.
V. Cooling systems like those described in Example II were operated with an alcohol as the cooling medium, with about 0.33% by weight of triethanolamine in the alcohol; with about 1.5% by weight of triethanolamine phosphate in the 55 alcohol; and with about 0.75% by weight of triethanolamine neutralized in part with about 1.5%
by weight of lard oil added to the alcohol. With the above additions, the corrosion produced in each case was negligible, as compared to that produced by the alcohol alone.
Mono or diethanolamine, mixtures of mono-, diand triethanolamine, or other hydroxy-alkylamines, such as propanolamine, etc., may be used instead of triethanolamine. Salts of inorganic and organic acids, such as the borates, acetates, formates and oxalates of hydroxy-alkylamines may be used instead of the phosphate, or the hydroxy-alkylamine may be partially or wholly neutralized with a fatty acid, such as stearic acid, oleic acid, palmitic acid, or mixtures of fatty acids, such as those found in lard oil and similar organic oils.
In each instance the result of the added inhibitor is to produce and maintain conditions in the solution which will render the liquid less corroslve to metal. Since an acidic condition is, in the main, the most prevalent in untreated liquids that are corrosive, the inhibitor added is in each case alkaline. The hydroxy-alkylamine whenused alone, neutralizes the undesirable acidity, but as has been stated, excessive alkalinity is undesirable, and somewhat more beneficial results are produced by partially neutralizing the alkaline hydroxy-alkylamine with an acid. It is necessary to use an acid which will form stable salts with the hydroxy-alkylamine, such salts being inert in respect to the liquid used, and producing a wholly stable condition in the final solution.
If the hydroxy-alkylamine is to be neutralized or partly neutralized by-means of lard oil or similar glycerides, excess amounts may be used inasmuch as the presence of the oil or the glycerides will not cause injurious corrosion in the system.
The concentration of the inhibitor in the liquid is dependent upon the liquid to be treated, the inhibitor to be used and the metals of which the liquid system is formed. The limits of concentration may, however, be determined by well knowntests. Thus, it has been determined that in a 35% solution by volume of ethylene glycol in water, the most satisfactory limits of concentration which will produce non-corrosive solutions are as follows:
1 Per cent 'Iriethanolamine 0.10 to 0.35 Triethanolamine phosphate 0.25 to 1.0
'Iriethanolamine lard oil 0.15 to 0.75 and 0.5 to
1.5 respectively. The above proportions refer to percent by weight of the composition.
:1 claim:
1. A liquid cooling medium for use in conjunction with a metal radiator, comprising an alcohol and a salt of an acid of the group consisting of oleic, palmitic and stearic and an ethanolamine,
said salt being present in suflicient quantity to inhibit the corrosion of said radiator.
HENRY L. COX.
US495302A 1930-11-12 1930-11-12 Corrosion inhibitor Expired - Lifetime US1992689A (en)

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Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2462694A (en) * 1946-10-09 1949-02-22 Du Pont Nonflammable hydraulic fluid
US2474325A (en) * 1943-04-07 1949-06-28 Jr Thomas T Rodgers Aqueous lubricant
US2566926A (en) * 1947-11-13 1951-09-04 Nat Distillers Prod Corp One-phase antirust liquid containing triethanolamine metaborate, triethanolamine, and a long-chain alcohol
US2566925A (en) * 1947-11-13 1951-09-04 Nat Distillers Prod Corp One-phase antirust liquid containing triethanolamine metaborate, triethanolamine, and mixed monoricinoleate esters
US2614981A (en) * 1950-04-03 1952-10-21 Standard Oil Dev Co Process for inhibiting corrosion in oil wells
US2614980A (en) * 1950-04-03 1952-10-21 Standard Oil Dev Co Process for inhibiting corrosion in oil wells
US2723233A (en) * 1952-12-10 1955-11-08 Exxon Research Engineering Co Method and composition for inhibiting corrosion
US2822409A (en) * 1954-04-29 1958-02-04 Gulf Research Development Co Distilling alcohols in presence of amines
US2951041A (en) * 1956-08-09 1960-08-30 Charles E Saunders Synthetic lubricant composition
US2988434A (en) * 1957-01-14 1961-06-13 Gulf Oil Corp Auxiliary fuels
US3046230A (en) * 1959-08-19 1962-07-24 Cities Service Res & Dev Co Antifreeze composition
US4389371A (en) * 1979-09-14 1983-06-21 Basf Wyandotte Corporation Process for inhibiting the corrosion of aluminum
US4452758A (en) * 1981-07-08 1984-06-05 Basf Wyandotte Corporation Compositions and process for inhibiting corrosion of aluminum
WO1984002146A1 (en) * 1982-11-22 1984-06-07 Ford Motor Canada Coatings comprising alkanolamine-carboxylic acid salts for friction material
US4526697A (en) * 1982-08-25 1985-07-02 Castrol Limited Improvements in the preparation of concentrates for high water based hydraulic fluids
US4539233A (en) * 1982-11-22 1985-09-03 Ford Motor Company Coating friction material with alkanolamine-carboxylic acid salts
US4726914A (en) * 1986-10-10 1988-02-23 International Minerals & Chemical Corp. Corrosion inhibitors
US9217087B2 (en) 2012-01-31 2015-12-22 Croda, Inc. Corrosion inhibitors

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2474325A (en) * 1943-04-07 1949-06-28 Jr Thomas T Rodgers Aqueous lubricant
US2462694A (en) * 1946-10-09 1949-02-22 Du Pont Nonflammable hydraulic fluid
US2566926A (en) * 1947-11-13 1951-09-04 Nat Distillers Prod Corp One-phase antirust liquid containing triethanolamine metaborate, triethanolamine, and a long-chain alcohol
US2566925A (en) * 1947-11-13 1951-09-04 Nat Distillers Prod Corp One-phase antirust liquid containing triethanolamine metaborate, triethanolamine, and mixed monoricinoleate esters
US2614981A (en) * 1950-04-03 1952-10-21 Standard Oil Dev Co Process for inhibiting corrosion in oil wells
US2614980A (en) * 1950-04-03 1952-10-21 Standard Oil Dev Co Process for inhibiting corrosion in oil wells
US2723233A (en) * 1952-12-10 1955-11-08 Exxon Research Engineering Co Method and composition for inhibiting corrosion
US2822409A (en) * 1954-04-29 1958-02-04 Gulf Research Development Co Distilling alcohols in presence of amines
US2951041A (en) * 1956-08-09 1960-08-30 Charles E Saunders Synthetic lubricant composition
US2988434A (en) * 1957-01-14 1961-06-13 Gulf Oil Corp Auxiliary fuels
US3046230A (en) * 1959-08-19 1962-07-24 Cities Service Res & Dev Co Antifreeze composition
US4389371A (en) * 1979-09-14 1983-06-21 Basf Wyandotte Corporation Process for inhibiting the corrosion of aluminum
US4452758A (en) * 1981-07-08 1984-06-05 Basf Wyandotte Corporation Compositions and process for inhibiting corrosion of aluminum
US4526697A (en) * 1982-08-25 1985-07-02 Castrol Limited Improvements in the preparation of concentrates for high water based hydraulic fluids
WO1984002146A1 (en) * 1982-11-22 1984-06-07 Ford Motor Canada Coatings comprising alkanolamine-carboxylic acid salts for friction material
US4539233A (en) * 1982-11-22 1985-09-03 Ford Motor Company Coating friction material with alkanolamine-carboxylic acid salts
US4726914A (en) * 1986-10-10 1988-02-23 International Minerals & Chemical Corp. Corrosion inhibitors
US9217087B2 (en) 2012-01-31 2015-12-22 Croda, Inc. Corrosion inhibitors

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