US2726215A - Rust inhibitors for aqueous systems - Google Patents

Rust inhibitors for aqueous systems Download PDF

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Publication number
US2726215A
US2726215A US283267A US28326752A US2726215A US 2726215 A US2726215 A US 2726215A US 283267 A US283267 A US 283267A US 28326752 A US28326752 A US 28326752A US 2726215 A US2726215 A US 2726215A
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Prior art keywords
corrosion
aqueous solutions
salt
acid
salts
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US283267A
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Donald T Jones
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Atlantic Richfield Co
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Atlantic Refining Co
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Priority to US283267A priority Critical patent/US2726215A/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
    • C23F11/12Oxygen-containing compounds
    • C23F11/124Carboxylic acids
    • C23F11/126Aliphatic acids

Definitions

  • This invention is directed to a method for suppressing the corrosion of metal surfaces in the presence of aqueous solutions. More particularly, this invention is directed to the suppression of corrosion which occurs when ferrous metals are contacted with water, or aqueous solutions containing dissolved salts or acids, or aqueous solutions which are admixed with non-aqueous solutions.
  • t is therefore the main object of the present invention to provide a process whereby the corrosion of metallic surfaces in the presence of aqueous solutions is materially inhibited.
  • Another object of the invention is to provide a method whereby the corrosion and rusting of ferrous metals in the presence of aqueous solutions is materially inhibited.
  • the invention is regarded as embracing the inhibition of the corrosion of metal surfaces in aqueous systems by introducing particular salts of certain dicarboxylic acids in said aqueous solutions.
  • alkalimetal salts such as, lithium, sodium, or potassium
  • alkaline earth metal salts such as,.barium, .calcium, or magnesium
  • the sebacic and azelaic acids which are employed to produce the salts used in the present invention maybe obtained inany manner well-known to the art.
  • a conventional method of preparing azelaic acid is by the oxidation of oleic acid
  • sebacic acid can be prepared by heating a castor oil soap with NaOI-I, followed by hydrolysis.
  • the eifectiveness of my composition in inhibitingthe corrosivity of aqueous solutions may-be better and more fully understood by reference .to certain tests which have been conducted, using both water and aqueous solutions containing substances known to promote corrosion of metal, such as, inorganic chlorides, or sulfates, and acetic or sulfuric acids.
  • the test procedure involved a measurement of the corrosive action of these aqueous solutions, as inhibited with the novel compositions of this invention, upon thoroughly cleaned and sanded steel panels and steel buttons, and a comparison thereof with the results obtained by subjecting identical test strips and buttons to the corrosive action of aqueous solutions not containing the anti-corrosion agent of the instant invention.
  • the steel buttons and panels were immersed in the above mentioned solutions at a temperature of about F. and observed daily for any evidence of rust.
  • the salts of this invention are capable of inhibiting corrosion of metal surfaces in aqueous solutions which are normally considered to be extremely corrosive-the lithium salt of azelaic acid being particularly effective.
  • Additional corrosion inhibitors or anti-rusting compounds may also be present in some instances, as long as there is no chemical interaction between the two additives which would tend to diminish the efiectiveness of the salts of the present invention.
  • corrosion protective compositions which are particularly valuable in an oil medium may be used in conjunction with the additive of this invention, subject to the aforementioned limitations.
  • I claim:' 1 A method for reducing the corrosion of metals in contact with aqueous solutions which comprises introducing into said aqueous solution a minor but corrosioninhibiting amount of a salt selected from the group consisting of an alkalimet'al salt and an alkaline earth metal salt of an acid selected from the group consisting of sebacic acid and azelaic acid.

Description

United States, Patent ce a 2,726,215 RUST INHIBITORS non AQUEOUS sYsrEMs Donald T. Jones, Springfield, Pa., assignor to The Atlantic Refining Company,'Philadelphia, Pa., a corporation of Pennsylvania N Drawing. Application April 19, 1952, Serial No. 283,267
' This invention is directed to a method for suppressing the corrosion of metal surfaces in the presence of aqueous solutions. More particularly, this invention is directed to the suppression of corrosion which occurs when ferrous metals are contacted with water, or aqueous solutions containing dissolved salts or acids, or aqueous solutions which are admixed with non-aqueous solutions.
The hazards of corrosion which are involved when aqueous solutions contact metal surfaces are well-known in every industry. Corrosion not only causes replacement of metals, but also often results ,in'darnage to products by contamination, shutdown of production, loss of ethciency, and mechanical failure by weakening of theequipment. In addition, corrosion often loosens finely divided metal oxides which may act as oxidation catalysts increasing the rate of deterioration of various organic compounds with which they come in contact, or may enter between moving parts of machinery where they act as abrasives. Even when corrosion proceeds at a rather slow rate, continued corrosion over an extended period of time can be extremely serious and involve a considerable expense in both repair and replacement.
The increased cost of nearly all metals'during the last decade as well as the difficulty of obtaining replacement equipment at any cost during periods of national emergency have stimulated efforts to minimize corrosion problems. The serious nature of the problem is reflected by the ever increasing amount of literature on both the broad and specific aspects of the subject.
One approach to the problem is to introduce a chemical into the fluid solution which is to contact the metal surface in an effort to minimize corrosion. Thousands of chemical compounds, both organic and inorganic, have been disclosed for this purpose, but the fact that none of these compounds has achieved universal acceptance in industry indicates that each chemical compound has only a limited field of application.
t is therefore the main object of the present invention to provide a process whereby the corrosion of metallic surfaces in the presence of aqueous solutions is materially inhibited. Another object of the invention is to provide a method whereby the corrosion and rusting of ferrous metals in the presence of aqueous solutions is materially inhibited. It is a further object of this invention to introduce specific organic salts into an aqueous solution to materially inhibit corrosion of metallic surfaces by said solution.
In its broadest conception the invention is regarded as embracing the inhibition of the corrosion of metal surfaces in aqueous systems by introducing particular salts of certain dicarboxylic acids in said aqueous solutions.
More particularly, it has been found that the alkali and alkali earth metal salts of certain dicarboxylic acids, namely, sebacic acid and azelaic acid, exhibit exceptional anti-corrosion powers when incorporated in an aqueous solution which is to contact a metal surface. The unexpectedness of this invention resides in the fact that,
2,726,215 Patented nee. ,1955
although various dicarboxylic acids have been alluded for use in the practice of the present invention are the alkalimetal salts, such as, lithium, sodium, or potassium, and the alkaline earth metal salts, such as,.barium, .calcium, or magnesium.
The sebacic and azelaic acids which are employed to produce the salts used in the present invention maybe obtained inany manner well-known to the art. The
production of these acids has been fully discussed in both the chemical and patent literature. For instance, a conventional method of preparing azelaic acid is by the oxidation of oleic acid, and sebacic acid can be prepared by heating a castor oil soap with NaOI-I, followed by hydrolysis.
Having described in detail the characteristics of the preferred anti-corrosion agent, the following examples Will illustrate certain of the numerous possible specific embodiments of the invention. The examples are intended to illustrate the invention and not to limit the same as it is defined more broadly in the appended claims.
The eifectiveness of my composition in inhibitingthe corrosivity of aqueous solutions may-be better and more fully understood by reference .to certain tests which have been conducted, using both water and aqueous solutions containing substances known to promote corrosion of metal, such as, inorganic chlorides, or sulfates, and acetic or sulfuric acids. The test procedure involved a measurement of the corrosive action of these aqueous solutions, as inhibited with the novel compositions of this invention, upon thoroughly cleaned and sanded steel panels and steel buttons, and a comparison thereof with the results obtained by subjecting identical test strips and buttons to the corrosive action of aqueous solutions not containing the anti-corrosion agent of the instant invention. The steel buttons and panels were immersed in the above mentioned solutions at a temperature of about F. and observed daily for any evidence of rust.
It was not possible to dissolved more than .05% of sebacic acid or more than .1% of azelaic in the distilled water. It will be observed from the data in the foregoing table that when sebacic acid'or azelaic acid were added to the distilled water, there was practically no corrosion inhibition. However, when the alkali or alkali earth metal salts of sebacic or azelaic acid were incorporated into the distilled water, corrosion inhibition was as much as 2000% greater. it is thusseen that when the quantity of the alkali or alkali earth metal salts of sebacic or azelaic acid become greater than the corresponding molar quantity of sebacic acid which can be dissolved, the rust inhibiting properties increased tremendously.
Another series of runs, similar to those shown in Table 1,, were conducted with aqueous solutions containing various substances known to promote rusting of iron and steel, such as, inorganic chlorides or sulfates and acetic or sulfuric acids. The results obtained in these runs are set forth in Table II below:
Table II Composition of Test Solutions Number of Days t 7 Prior to Rust Inhibiting Agent Rust Promoting Agent Busting 3% Lithium Azelate Synthetic Sea Water 20+ 3% Sodium A'mlntp (in 7 None do 1 3% Lithium Azelete '0.1H%IzSO4 in Distilled 20+ 7 2 0.8% Barium azelate.- do 7+ 3.0% Sodium Azelate. do. 20+ None .do 1 3% Lithium Azclate 0.1% Acetic Acid in Dis- 20% tilled H20. 0.8% Barium Azelate (1 7+ 3% Sodium Azelate 10 None 1 Synthetic sea water: 11.0 g. MgClzfiHzO, 1.2 g. CaOlz, 4.0 g. NaaSOa, 25.0 g. NaCl per liter of distilled water.
It will be observed from the data presented in the foregoing table that the salts of this invention are capable of inhibiting corrosion of metal surfaces in aqueous solutions which are normally considered to be extremely corrosive-the lithium salt of azelaic acid being particularly effective.
Additional corrosion inhibitors or anti-rusting compounds may also be present in some instances, as long as there is no chemical interaction between the two additives which would tend to diminish the efiectiveness of the salts of the present invention. Thus, in instances where a metal surface is to contact a fluid medium which contains both water and oil, corrosion protective compositions which are particularly valuable in an oil medium may be used in conjunction with the additive of this invention, subject to the aforementioned limitations.
I claim:' 1. A method for reducing the corrosion of metals in contact with aqueous solutions which comprises introducing into said aqueous solution a minor but corrosioninhibiting amount of a salt selected from the group consisting of an alkalimet'al salt and an alkaline earth metal salt of an acid selected from the group consisting of sebacic acid and azelaic acid.
2. The method according to claim 1, wherein the salt is an alkali metal salt of azelaic acid.
3. The method according to claim 2, wherein the salt is lithium azelate.
4. The method according to claim 1, wherein the salt is sodium azelate.
5. The method according to claim 1, wherein the salt is an alkali earth metal salt of azelaic acid.
6. The method according to claim 5, wherein the salt is barium azelate.
References Cited in the file of this patent UNITED STATES PATENTS

Claims (1)

1. A METHOD FOR REDUCING THE CORROSION OF METALS IN CONTACT WITH AQUEOUS SOLUTIONS WHICH COMPRISES INTRODUCING INTO SAID AQUEOUS SOLUTION A MINOR BUT CORROSIONINHIBITING AMOUNT OF A SALT SELECTED FROM THE GROUP CONSISTING OF AN ALKALI METAL SALT AND AN ALKALINE EARTH METAL SALT OF AN ACID SELECTED FROM THE GROUP CONSISTING OF SEBACIC ACID AZELAIC ACID.
US283267A 1952-04-19 1952-04-19 Rust inhibitors for aqueous systems Expired - Lifetime US2726215A (en)

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Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3223497A (en) * 1961-08-31 1965-12-14 Standard Oil Co Gasoline composition containing a multipurpose additive
DE1243214B (en) * 1962-01-29 1967-06-29 Carrier Corp Corrosion protection for absorption refrigeration machines working with salt solutions
US3405072A (en) * 1966-01-05 1968-10-08 Continental Can Co Method of inhibiting corrosion of aqueous mediums by addition of lithium salts of organic acids
DE1285835B (en) * 1963-02-06 1968-12-19 Geigy Ag J R Corrosion protection agent for metal surfaces that are in contact with liquid media
US4135934A (en) * 1975-08-29 1979-01-23 National Research Development Corporation Metal coating compositions
US4192769A (en) * 1978-05-12 1980-03-11 The Lubrizol Corporation Rust inhibitor additive compositions, method of making, and aqueous fluids containing the same
US4217142A (en) * 1975-08-29 1980-08-12 National Research Development Corporation Metal coating compositions
US4250042A (en) * 1979-04-16 1981-02-10 The Lubrizol Corporation Corrosion inhibition in well-drilling operations using aqueous systems containing ammonium carboxylates
EP0029892A1 (en) * 1979-12-01 1981-06-10 Chemische Werke Hüls Ag Use of alcali or amino salts of a mixture of 2- and 3-alkyl-adipinic acids as corrosion inhibitor
US4374174A (en) * 1981-02-12 1983-02-15 Daubert Industries, Inc. Composition and sheet materials for inhibiting corrosion of metals
US4454050A (en) * 1983-03-21 1984-06-12 Pennwalt Corporation Aqueous release agent and lubricant
FR2538406A1 (en) * 1982-12-27 1984-06-29 Bp Chimie Sa PROCESS FOR TREATING AQUEOUS FLUIDS TO REDUCE THE CORROSION OF METALS IN CONTACT WITH THEM
US4561990A (en) * 1984-10-04 1985-12-31 Texaco Inc. High lead solder corrosion inhibitors
US4578205A (en) * 1985-02-01 1986-03-25 Texaco, Inc. Use of methylene azelaic acid as a corrosion inhibitor
US4584119A (en) * 1985-04-19 1986-04-22 Texaco, Inc. Naphthalene dicarboxylic acid salts as corrosion inhibitors
US4588513A (en) * 1984-11-19 1986-05-13 Texaco, Inc. Non-borate, non-phosphate antifreeze formulations containing dibasic acid salts as corrosion inhibitors
US4592853A (en) * 1985-05-08 1986-06-03 Texaco Inc. Dicyclopentadiene dicarboxylic acid salts as corrosion inhibitors
US4946616A (en) * 1988-11-14 1990-08-07 The Dow Chemical Company Heat transfer fluids containing dicarboxylic acid mixtures as corrosion inhibitors
US5240631A (en) * 1991-11-13 1993-08-31 Arco Chemical Technology, L.P. Antifreeze formulation containing phosphorous acid
US5422026A (en) * 1990-12-14 1995-06-06 Arco Chemical Technology, L.P. Phosphate-free antifreeze formulation
US5651916A (en) * 1995-08-23 1997-07-29 Prestone Products Corporation Process for the preparation of a propylene glycol antifreeze containing an alkali metal silicate
US5741436A (en) * 1995-12-05 1998-04-21 Prestone Products Corp. Antifreeze concentrates and compositions comprising neodecanoic acid corrosion inhibitors
US6585150B1 (en) 2000-10-12 2003-07-01 International Business Machines Corporation Solder protective coating and fluxless joining of flip chip devices on laminates with plated solder
US20070131898A1 (en) * 2005-12-12 2007-06-14 Sung Choon Yoo Antifreeze composition
US20140219994A1 (en) * 2011-06-29 2014-08-07 Zhendong Liu Molybdate-free sterilizing and pasteurizing solutions

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2363516A (en) * 1942-12-03 1944-11-28 Standard Oil Co California Compounded hydrocarbon oils
US2426496A (en) * 1944-03-21 1947-08-26 Shell Dev Corrosion protecting compositions

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2363516A (en) * 1942-12-03 1944-11-28 Standard Oil Co California Compounded hydrocarbon oils
US2426496A (en) * 1944-03-21 1947-08-26 Shell Dev Corrosion protecting compositions

Cited By (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3223497A (en) * 1961-08-31 1965-12-14 Standard Oil Co Gasoline composition containing a multipurpose additive
DE1243214B (en) * 1962-01-29 1967-06-29 Carrier Corp Corrosion protection for absorption refrigeration machines working with salt solutions
DE1285835B (en) * 1963-02-06 1968-12-19 Geigy Ag J R Corrosion protection agent for metal surfaces that are in contact with liquid media
US3405072A (en) * 1966-01-05 1968-10-08 Continental Can Co Method of inhibiting corrosion of aqueous mediums by addition of lithium salts of organic acids
US4135934A (en) * 1975-08-29 1979-01-23 National Research Development Corporation Metal coating compositions
US4217142A (en) * 1975-08-29 1980-08-12 National Research Development Corporation Metal coating compositions
US4192769A (en) * 1978-05-12 1980-03-11 The Lubrizol Corporation Rust inhibitor additive compositions, method of making, and aqueous fluids containing the same
US4250042A (en) * 1979-04-16 1981-02-10 The Lubrizol Corporation Corrosion inhibition in well-drilling operations using aqueous systems containing ammonium carboxylates
EP0029892A1 (en) * 1979-12-01 1981-06-10 Chemische Werke Hüls Ag Use of alcali or amino salts of a mixture of 2- and 3-alkyl-adipinic acids as corrosion inhibitor
US4414125A (en) * 1979-12-01 1983-11-08 Chemische Werke Huels Aktiengesellschaft Alkali metal or amine salts of a mixture of 2- and 3-alkyladipic acids as corrosion inhibitors
US4374174A (en) * 1981-02-12 1983-02-15 Daubert Industries, Inc. Composition and sheet materials for inhibiting corrosion of metals
FR2538406A1 (en) * 1982-12-27 1984-06-29 Bp Chimie Sa PROCESS FOR TREATING AQUEOUS FLUIDS TO REDUCE THE CORROSION OF METALS IN CONTACT WITH THEM
EP0112756A1 (en) * 1982-12-27 1984-07-04 BP Chimie Société Anonyme Process for treating aqueous fluids to reduce the corrosion of metals with which they are in contact
US4869841A (en) * 1982-12-27 1989-09-26 Bp Chimie S.A. Process for the treatment of aqueous fluids to reduce corrosion comprising dicarboxylic aliphatic acid salt and polyol
US4454050A (en) * 1983-03-21 1984-06-12 Pennwalt Corporation Aqueous release agent and lubricant
US4561990A (en) * 1984-10-04 1985-12-31 Texaco Inc. High lead solder corrosion inhibitors
US4588513A (en) * 1984-11-19 1986-05-13 Texaco, Inc. Non-borate, non-phosphate antifreeze formulations containing dibasic acid salts as corrosion inhibitors
US4578205A (en) * 1985-02-01 1986-03-25 Texaco, Inc. Use of methylene azelaic acid as a corrosion inhibitor
EP0189833A1 (en) * 1985-02-01 1986-08-06 Texaco Development Corporation Use of methylene azelaic acid as a corrosion inhibitor
US4584119A (en) * 1985-04-19 1986-04-22 Texaco, Inc. Naphthalene dicarboxylic acid salts as corrosion inhibitors
US4592853A (en) * 1985-05-08 1986-06-03 Texaco Inc. Dicyclopentadiene dicarboxylic acid salts as corrosion inhibitors
US4946616A (en) * 1988-11-14 1990-08-07 The Dow Chemical Company Heat transfer fluids containing dicarboxylic acid mixtures as corrosion inhibitors
US5422026A (en) * 1990-12-14 1995-06-06 Arco Chemical Technology, L.P. Phosphate-free antifreeze formulation
US5240631A (en) * 1991-11-13 1993-08-31 Arco Chemical Technology, L.P. Antifreeze formulation containing phosphorous acid
US5651916A (en) * 1995-08-23 1997-07-29 Prestone Products Corporation Process for the preparation of a propylene glycol antifreeze containing an alkali metal silicate
US5741436A (en) * 1995-12-05 1998-04-21 Prestone Products Corp. Antifreeze concentrates and compositions comprising neodecanoic acid corrosion inhibitors
US6585150B1 (en) 2000-10-12 2003-07-01 International Business Machines Corporation Solder protective coating and fluxless joining of flip chip devices on laminates with plated solder
US20030178473A1 (en) * 2000-10-12 2003-09-25 International Business Machines Corporation Solder protective coating and fluxless joining of flip chip devices on laminates with plated solder
US6921015B2 (en) 2000-10-12 2005-07-26 International Business Machines Corporation Solder protective coating and fluxless joining of flip chip devices on laminates with plated solder
US20070131898A1 (en) * 2005-12-12 2007-06-14 Sung Choon Yoo Antifreeze composition
US20140219994A1 (en) * 2011-06-29 2014-08-07 Zhendong Liu Molybdate-free sterilizing and pasteurizing solutions
US9873535B2 (en) * 2011-06-29 2018-01-23 Genral Electric Company Molybdate-free sterilizing and pasteurizing solutions

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