[go: up one dir, main page]

US2913408A - Corrosion inhibitors for ferrous metals in aqueous solutions of non-oxidizing acids - Google Patents

Corrosion inhibitors for ferrous metals in aqueous solutions of non-oxidizing acids Download PDF

Info

Publication number
US2913408A
US2913408A US631045A US63104556A US2913408A US 2913408 A US2913408 A US 2913408A US 631045 A US631045 A US 631045A US 63104556 A US63104556 A US 63104556A US 2913408 A US2913408 A US 2913408A
Authority
US
United States
Prior art keywords
acid
ferrous metals
aqueous solutions
corrosion inhibitors
inhibitor
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
Application number
US631045A
Inventor
Charles T Pumpelly
Joseph L Wasco
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
Original Assignee
Dow Chemical Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dow Chemical Co filed Critical Dow Chemical Co
Priority to US631045A priority Critical patent/US2913408A/en
Application granted granted Critical
Publication of US2913408A publication Critical patent/US2913408A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • 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
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors
    • C23G1/068Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors compounds containing a C=C bond
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S507/00Earth boring, well treating, and oil field chemistry
    • Y10S507/939Corrosion inhibitor

Definitions

  • This invention relates to corrosion inhibitors for use in aqueous solutions of non-oxidizing acids to inhibit the corrosion of ferrous metals by such acids.
  • the inhibitors of the invention are acetylenic alcohols corresponding to the formula R CHEC-CHrJl-OH wherein the R substituents together contain 4 to 12 carbon atoms and are independently Selected from the group consisting of hydrogen, alkyl radicals containing 1 to 8 carbon atoms and which may be joined together to form a cycloalkyl ring containing 5 to 6 carbon atoms, phenyl and chlorophenyl radicals.
  • an acetylenic alcohol corresponding to the above formula is dissolved or dispersed in the acid the corrosive action of which is to be inhibited.
  • aqueous acid we mean a composition comprising acid and water and do not mean to exclude the presence of other substances.
  • ferrous metals we mean iron, steel, stainless steel and, in general, any metal comprising a major proportion of iron.
  • the inhibitors of the invention are effective not only at ordinary temperatures but also at elevated temperatures. All are effective at 150 degrees and some at 200 degrees F. Moreover, they are effective in various concentrations of acids, even including hydrochloric acid up to 37 percent, that is, commercial concentrated acid.
  • inhibitors are particularly useful include metal-pickling, cleaning and polishing baths, oil well-acidizing solutions, boiler-cleaning compositions and the like.
  • the inhibitors of this invention are either commercially available or are easily made from commercially available intermediates.
  • the alcohols are easily prepared from propargyl bromide and the appropriate carbonyl compound by well known methods, such as that of Henbest et al., J. Chem. Soc., 1949, 2696-2700.
  • the inhibitor When the inhibitor is not completely soluble in the aqueous acid in which it is to be used, as when the compounds of Examples 3-6 are desired to be used in amounts exceeding their solubility, it is usually advantageous to incorporate into the inhibitor-acid mixture a small amount of a suitable surfactant whereby the inhibitor is solubilized and/ or dispersed in the acid, thereby greatly increasing its effectiveness.
  • a suitable surfactant are those that are stable in acid media under the conditions of use, the non-ionic surfactants being preferred for this reason.
  • An aqueous solution of a non-oxidizing acid containing an effective amount of a corrosion inhibitor consisting solely of a compound corresponding to the formula wherein the R substituents together contain 4 to 12 carbon atoms and are independently selected from the group consisting of hydrogen, phenyl, chlorophenyl, alkyl groups containing 1 to 8 carbon atoms each and parts of a cycloalkyl ring containing 5 to 6 carbon atoms.
  • a solution as defined in claim 7 wherein the in hibitor is 4-methyl-1-heptyn-4-ol.
  • a process for inhibiting the corrosion of ferrous metals in contact with aqueous non-oxidizing acid consisting essentially of maintaining in said acid an efiective amount of a corrosion inhibitor consisting solely of a compound as defined in claim 1.”

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General 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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Description

United States Patent CORROSION INHIBITORS FOR FERROUS lVIETALS t gunous SOLUTIONS OF NON-OXIDIZING Charles T. Pumpelly and Joseph L. Wasco, Midland,
Mich., assignors to The Dow Chemical Company, Midland, Mich., a corporation of Delaware No Drawing. Application December 28, 1956 Serial No. 631,045
14 Claims. (Cl. 252-855) This invention relates to corrosion inhibitors for use in aqueous solutions of non-oxidizing acids to inhibit the corrosion of ferrous metals by such acids.
The inhibitors of the invention are acetylenic alcohols corresponding to the formula R CHEC-CHrJl-OH wherein the R substituents together contain 4 to 12 carbon atoms and are independently Selected from the group consisting of hydrogen, alkyl radicals containing 1 to 8 carbon atoms and which may be joined together to form a cycloalkyl ring containing 5 to 6 carbon atoms, phenyl and chlorophenyl radicals.
According to the invention an acetylenic alcohol corresponding to the above formula is dissolved or dispersed in the acid the corrosive action of which is to be inhibited.
By aqueous acid we mean a composition comprising acid and water and do not mean to exclude the presence of other substances. By ferrous metals we mean iron, steel, stainless steel and, in general, any metal comprising a major proportion of iron.
Only a small amount of the inhibitor is needed. As little as a few thousandths of 1 percent, based on the aqueous acid, significantly reduces the corrosion of ferrous metals exposed to the acid. The degree of inhibition increases with the concentration of the inhibitor up to a level of about 1 percent. Beyond this point little added protection of the metal is obtained by the use of more inhibitor. We generally prefer to use our inhibitors at a level of about 0.1 to 0.4 percent, this amount being adequate for most purposes.
The inhibitors of the invention are effective not only at ordinary temperatures but also at elevated temperatures. All are effective at 150 degrees and some at 200 degrees F. Moreover, they are effective in various concentrations of acids, even including hydrochloric acid up to 37 percent, that is, commercial concentrated acid.
Applications in which the inhibitors are particularly useful include metal-pickling, cleaning and polishing baths, oil well-acidizing solutions, boiler-cleaning compositions and the like.
The inhibitors of this invention are either commercially available or are easily made from commercially available intermediates.
The alcohols are easily prepared from propargyl bromide and the appropriate carbonyl compound by well known methods, such as that of Henbest et al., J. Chem. Soc., 1949, 2696-2700.
In order to demonstrate the effectiveness of our inhibitors, a series of tests was run in which 0.4 percent of the inhibitor was put into a 10 percent aqueous solution of hydrochloric acid held at 150 degrees F. and a coupon of the metal to be tested was suspended in the solution for 16 hours. Thereafter the coupon was 2,913,408 Patented Nov. 17, 1959 cleaned, dried and weighed to determine the amount of metal dissolved by the acid. The results obtained in a series of such tests in which mild steel was used are shown in the following table.
a In the inhibitors of Examples 7 and 8 the 2 R's are joined to form cyclohexyl and eyclopentyl groups, respectively.
Results similar to those shown in the above table are obtained when other non-oxidizing acids, such as sulfuric, phosphoric and acetic acid, are used instead of hydrochloric acid; when other concentrations of the acid up to the commercial concentrated acid (37 percent) are used; and when other ferrous metals are used instead of mild steel. The inhibitors are also effective at elevated temperatures up to about degrees F.
When the inhibitor is not completely soluble in the aqueous acid in which it is to be used, as when the compounds of Examples 3-6 are desired to be used in amounts exceeding their solubility, it is usually advantageous to incorporate into the inhibitor-acid mixture a small amount of a suitable surfactant whereby the inhibitor is solubilized and/ or dispersed in the acid, thereby greatly increasing its effectiveness. In general, the suitable surfactants are those that are stable in acid media under the conditions of use, the non-ionic surfactants being preferred for this reason.
We claim:
1. An aqueous solution of a non-oxidizing acid containing an effective amount of a corrosion inhibitor consisting solely of a compound corresponding to the formula wherein the R substituents together contain 4 to 12 carbon atoms and are independently selected from the group consisting of hydrogen, phenyl, chlorophenyl, alkyl groups containing 1 to 8 carbon atoms each and parts of a cycloalkyl ring containing 5 to 6 carbon atoms.
2. A solution as defined in claim 1 wherein at least one of the R groups is an alkyl group.
3. A solution as defined in claim 1 wherein the two R substituents are joined to form a cycloalkyl group.
4. A solution as defined in claim 1 wherein the inhibitor is 2-(p-chlorophenyl)-4-pentyn-2-ol.
5. A solution as defined in claim 1 wherein the acid is hydrochloric acid.
6. solution as defined in claim 2 wherein one R is a I i 1 hydrogen and the other is an alkyl group.
7. A solution as defined in claim 2 wherein both R groups are alkyl groups. p
8. A solution as defined in claim 3 wherein the inhibitor is 1-(2-propynyl)cyclohexanol.
9. A solution as defined in claim 3 whereinthe-im hibitor is 1-(2-propynyl)cyclopentanol.
10. A solution as defined in claim 6 wherein the inhibitor is 1-heptyn-4-ol.
11. A solution as defined in claim 7 wherein the in hibitor is 4-methyl-1-heptyn-4-ol.
12. A process for inhibiting the corrosion of ferrous metals in contact with aqueous non-oxidizing acid, said process consisting essentially of maintaining in said acid an efiective amount of a corrosion inhibitor consisting solely of a compound as defined in claim 1."
4 t 13. A process as defined in claim 12 wherein the inhibitor is 1-(2-propynyl)cyclohexanol.
14. A process as defined in claim 13 wherein the acid is hydrochloric acid.
References Cited in the file of this patent 'UNITED STATES PATENTS Mascre May 30, 1939 2,204,597 Humphreys et a1. June 18,1940 2,355,599 Walker Aug. 8, 1944 "2,474,603 Viles et a1. June 28, 1949 2,564,757 Glasebrook Aug. 21, 1951 2,603,622 Berger July 15, 1952 2,806,067 Monroe et al. Sept. 10, 1957 2,814,593
Beiswanger et al. Nov. 26, 1957

Claims (1)

1. AN AQUEOUS SOLUTION OF A NON-OXIDIZING ACID CONCTAINING AN EFFECTIVE AMOUNT OF A CORROSION INHIBITOR CONSISTING SOLELY OF A COMPOUND CORRSPONDING TO THE FORMULA
US631045A 1956-12-28 1956-12-28 Corrosion inhibitors for ferrous metals in aqueous solutions of non-oxidizing acids Expired - Lifetime US2913408A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US631045A US2913408A (en) 1956-12-28 1956-12-28 Corrosion inhibitors for ferrous metals in aqueous solutions of non-oxidizing acids

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US631045A US2913408A (en) 1956-12-28 1956-12-28 Corrosion inhibitors for ferrous metals in aqueous solutions of non-oxidizing acids

Publications (1)

Publication Number Publication Date
US2913408A true US2913408A (en) 1959-11-17

Family

ID=24529548

Family Applications (1)

Application Number Title Priority Date Filing Date
US631045A Expired - Lifetime US2913408A (en) 1956-12-28 1956-12-28 Corrosion inhibitors for ferrous metals in aqueous solutions of non-oxidizing acids

Country Status (1)

Country Link
US (1) US2913408A (en)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2975125A (en) * 1957-03-01 1961-03-14 Amchem Prod Inhibitor compositions
US3047511A (en) * 1959-08-24 1962-07-31 Dow Chemical Co Mineral acid inhibitor
US3049496A (en) * 1959-04-30 1962-08-14 Dow Chemical Co Propargyl compounds as corrosion inhibitors
US3077454A (en) * 1960-07-14 1963-02-12 Dow Chemical Co Compositions for inhibiting corrosion
US3077453A (en) * 1961-09-01 1963-02-12 Dow Chemical Co Corrosion inhibition
US3079345A (en) * 1959-04-30 1963-02-26 Dow Chemical Co Propargyl compounds as corrosion inhibitors
US3095381A (en) * 1959-08-28 1963-06-25 Air Reduction Cleaning compositions
US3107221A (en) * 1958-04-18 1963-10-15 Dow Chemical Co Corrosion inhibitor composition
US3108069A (en) * 1961-01-26 1963-10-22 Dow Chemical Co Ethynyl compounds for use in the inhibition of silicate swelling
US3231507A (en) * 1960-04-21 1966-01-25 Dow Chemical Co Corrosion inhibitors for aqueous acids
US3249548A (en) * 1958-10-31 1966-05-03 Cumberland Chemical Corp Corrosion inhibiting composition comprising 4-ethyl-1-octyn-3-ol
US3979311A (en) * 1974-05-30 1976-09-07 Universal Oil Products Company Corrosion inhibitor compositions
US4039336A (en) * 1975-12-03 1977-08-02 Exxon Research And Engineering Company Diacetylenic alcohol corrosion inhibitors
WO2017066571A1 (en) 2015-10-15 2017-04-20 Agios Pharmaceuticals, Inc. Combination therapy for treating malignancies
WO2020092894A1 (en) 2018-11-02 2020-05-07 Celgene Corporation Solid forms of 2-methyl-1-[(4-[6-(trifluoromethyl) pyridin-2-yl]-6-{[2-(trifluoromethyl)pyridin-4-yl]amino}-1,3,5-triazin-2-yl) amino]propan-2-ol
EP3692983A1 (en) 2008-05-15 2020-08-12 Celgene Corporation Oral formulations of cytidine analogs and methods of use thereof
US11591511B2 (en) 2018-05-11 2023-02-28 Fluid Energy Group Ltd Methods for stimulating a hydrocarbon-bearing formation by perforating a wellbore and introducing and acidic composition in the wellbore
US12241021B2 (en) 2018-05-11 2025-03-04 Dorf Ketal Chemicals Fze Method for fracking of simulation of hydrocarbon bearing formation

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2160406A (en) * 1939-04-29 1939-05-30 Lambiotte Freres Ets Product for inhibiting the attack on metals by acids or salts and its applications
US2204597A (en) * 1937-02-23 1940-06-18 Standard Oil Co Compounded lubricant
US2355599A (en) * 1941-01-23 1944-08-08 Du Pont Acid metal treating baths
US2474603A (en) * 1946-12-20 1949-06-28 Standard Oil Dev Co Inhibition of corrosion in wells
US2564757A (en) * 1950-06-03 1951-08-21 Hercules Powder Co Ltd Corrosion inhibitor composition
US2603622A (en) * 1948-10-01 1952-07-15 Berger Heinrich Halogen containing resin stabilized with an acetylene alcohol
US2806067A (en) * 1956-08-02 1957-09-10 Dow Chemical Co Alpha-ethynyl-2, 4, 6-trimethyl-3-cyclohexene-1-methanol
US2814593A (en) * 1953-12-18 1957-11-26 Gen Aniline & Film Corp Corrosion inhibition

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2204597A (en) * 1937-02-23 1940-06-18 Standard Oil Co Compounded lubricant
US2160406A (en) * 1939-04-29 1939-05-30 Lambiotte Freres Ets Product for inhibiting the attack on metals by acids or salts and its applications
US2355599A (en) * 1941-01-23 1944-08-08 Du Pont Acid metal treating baths
US2474603A (en) * 1946-12-20 1949-06-28 Standard Oil Dev Co Inhibition of corrosion in wells
US2603622A (en) * 1948-10-01 1952-07-15 Berger Heinrich Halogen containing resin stabilized with an acetylene alcohol
US2564757A (en) * 1950-06-03 1951-08-21 Hercules Powder Co Ltd Corrosion inhibitor composition
US2814593A (en) * 1953-12-18 1957-11-26 Gen Aniline & Film Corp Corrosion inhibition
US2806067A (en) * 1956-08-02 1957-09-10 Dow Chemical Co Alpha-ethynyl-2, 4, 6-trimethyl-3-cyclohexene-1-methanol

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2975125A (en) * 1957-03-01 1961-03-14 Amchem Prod Inhibitor compositions
US3107221A (en) * 1958-04-18 1963-10-15 Dow Chemical Co Corrosion inhibitor composition
US3249548A (en) * 1958-10-31 1966-05-03 Cumberland Chemical Corp Corrosion inhibiting composition comprising 4-ethyl-1-octyn-3-ol
US3079345A (en) * 1959-04-30 1963-02-26 Dow Chemical Co Propargyl compounds as corrosion inhibitors
US3049496A (en) * 1959-04-30 1962-08-14 Dow Chemical Co Propargyl compounds as corrosion inhibitors
US3047511A (en) * 1959-08-24 1962-07-31 Dow Chemical Co Mineral acid inhibitor
US3095381A (en) * 1959-08-28 1963-06-25 Air Reduction Cleaning compositions
US3231507A (en) * 1960-04-21 1966-01-25 Dow Chemical Co Corrosion inhibitors for aqueous acids
US3077454A (en) * 1960-07-14 1963-02-12 Dow Chemical Co Compositions for inhibiting corrosion
US3108069A (en) * 1961-01-26 1963-10-22 Dow Chemical Co Ethynyl compounds for use in the inhibition of silicate swelling
US3077453A (en) * 1961-09-01 1963-02-12 Dow Chemical Co Corrosion inhibition
US3979311A (en) * 1974-05-30 1976-09-07 Universal Oil Products Company Corrosion inhibitor compositions
US4039336A (en) * 1975-12-03 1977-08-02 Exxon Research And Engineering Company Diacetylenic alcohol corrosion inhibitors
EP3692983A1 (en) 2008-05-15 2020-08-12 Celgene Corporation Oral formulations of cytidine analogs and methods of use thereof
EP3782612A1 (en) 2008-05-15 2021-02-24 Celgene Corporation Oral formulations of cytidine analogs and methods of use thereof
WO2017066571A1 (en) 2015-10-15 2017-04-20 Agios Pharmaceuticals, Inc. Combination therapy for treating malignancies
US11591511B2 (en) 2018-05-11 2023-02-28 Fluid Energy Group Ltd Methods for stimulating a hydrocarbon-bearing formation by perforating a wellbore and introducing and acidic composition in the wellbore
US12018210B2 (en) 2018-05-11 2024-06-25 Dorf Ketal Chemicals Fze Methods for stimulating a hydrocarbon-bearing formation by perforating a wellbore and introducing an acidic composition in the wellbore
US12241021B2 (en) 2018-05-11 2025-03-04 Dorf Ketal Chemicals Fze Method for fracking of simulation of hydrocarbon bearing formation
US12497557B2 (en) 2018-05-11 2025-12-16 Dorf Ketal Chemicals Fze Methods for stimulating a hydrocarbon-bearing formation by perforating a wellbore and introducing an acidic composition in the wellbore
WO2020092894A1 (en) 2018-11-02 2020-05-07 Celgene Corporation Solid forms of 2-methyl-1-[(4-[6-(trifluoromethyl) pyridin-2-yl]-6-{[2-(trifluoromethyl)pyridin-4-yl]amino}-1,3,5-triazin-2-yl) amino]propan-2-ol

Similar Documents

Publication Publication Date Title
US2913408A (en) Corrosion inhibitors for ferrous metals in aqueous solutions of non-oxidizing acids
US3107221A (en) Corrosion inhibitor composition
US4104303A (en) Acid inhibitor composition and process in hydrofluoric acid chemical cleaning
US2956956A (en) Inhibitors for acid solutions employed in the surface treatment of metals
US3079345A (en) Propargyl compounds as corrosion inhibitors
US3642652A (en) Diethanolamine boric esters rust inhibitors
US2606873A (en) Composition for removing scale deposits from ferrous metal surfaces
US3049496A (en) Propargyl compounds as corrosion inhibitors
Wachter Sodium Nitrite as Corrosion Inhibitor for Water.
US4640786A (en) Phosphonium salt-containing corrosion inhibitors for high density brines
US3094490A (en) Inhibitor composition and method of inhibiting acid attack on metal in the acidizing f wells
US3245915A (en) Composition and method of inhibiting corrosion of metal surfaces in contact with aqueous surface active solutions
US3231507A (en) Corrosion inhibitors for aqueous acids
US2955083A (en) Corrosion inhibitors in well treating compositions
US2993864A (en) Ethynylcyclohexyl compounds as corrosion inhibitors
US2993863A (en) Halogenated propargyl alcohols as corrosion inhibitors
US4206233A (en) Microbiocidal quaternaries of halogen derivatives of alkynoxymethyl amines
US3047510A (en) Corrosion inhibiting compositions and process
US3030311A (en) Mineral acid inhibitors
US2624706A (en) Noncorrosive fire extinguishing composition
US3819527A (en) Composition and method for inhibiting acid attack of metals
US2993862A (en) Acetylenic glycols as corrosion inhibitors
US1847711A (en) Noncorrosive alcoholic solution
US2970113A (en) Stabilization of 1, 1, 1-trichloroethane
US2164565A (en) Rust inhibitor