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US2993862A - Acetylenic glycols as corrosion inhibitors - Google Patents

Acetylenic glycols as corrosion inhibitors Download PDF

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Publication number
US2993862A
US2993862A US601641A US60164156A US2993862A US 2993862 A US2993862 A US 2993862A US 601641 A US601641 A US 601641A US 60164156 A US60164156 A US 60164156A US 2993862 A US2993862 A US 2993862A
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United States
Prior art keywords
corrosion inhibitors
hydrochloric acid
corrosion
inhibitor
acetylenic glycols
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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
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US601641A
Inventor
Roger F Monroe
Fred J Lowes
Gerald L Foster
Billy D Oakes
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Dow Chemical Co
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Dow Chemical Co
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Priority to US601641A priority Critical patent/US2993862A/en
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Publication of US2993862A publication Critical patent/US2993862A/en
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Expired - Lifetime legal-status Critical Current

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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
    • 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
    • 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
    • C23F11/04Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in markedly acid liquids
    • 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
    • Y10S507/933Acidizing or formation destroying
    • Y10S507/934Acidizing or formation destroying with inhibitor

Definitions

  • This invention relates to corrosion inhibitors for use in aqueous hydrochloric acid to inhibit the corrosion of iron, steel, nickel or ferrous alloy metals exposed to said aqueous acid.
  • acetylenic glycols specifically, those having the formula R R Rd0E0-GE0d-R H H wherein R is a radical selected from the group consisting of H and CH are potent corrosion inhibitors and, as such, are particularly efiective in protecting iron, steel, [ferrous alloys and nickel from the corrosive attack of aqueous hydrochloric acid.
  • aqueous hydrochloric acid we mean HCl in the presence of a significant amount of Water and do not mean to exclude the presence of other substances.
  • the inhibitors are simply dissolved in the hydrochloric acid solution the corrosive action of which is to be inhibited. Only a small amount of inhibitor is required. As little as a few thousandths of .1 percent, based on the acid solution, significantly reduces the corrosion of iron and nickel exposed to the acid. The degree if inhibition increases with the concentration of the inhibitor up to a concentration of about 1 percent. Beyond this point there is little advantage in using more inhibitor.
  • the inhibitors of the invention are efiective not only at ordinary temperatures but also at elevated temperatures, up to the point at which the inhibitors decompose. They are effective in all concentrations of hydrochloric acid up to and including commercial concentrated acid (about 36 percent). Applications in which they are particularly useful include metal-cleaning baths, oil welltreating acids, boiler-cleaning solutions and the like.
  • Aqueous hydrochloric acid containing about 5 to 36% concentration, by weight, and, as the sole active corrosion inhibitor therefor an efiective amount of a compound having the formula H H wherein R is a radical selected from the group consisting of H and --CH 2.
  • R is H.
  • a solution as in claim 1 wherein the concentration of the inhibitor is from a few thousandths percent to about one percent, by weight.
  • a process for inhibiting the corrosion of a metal of the group consisting of iron, steel, nickel and ferrous alloys by aqueous hydrochloric acid in contact therewith comprising maintaining in said acid a small but effective concentration of the inhibitor having the formula R RJJ- EC -CEO-ER H H wherein R is a radical selected from the group consisting of H and CH3.
  • concentration of inhibitor is from a iew thousandths percent to about 1 percent, by weight.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Description

United States Patent 2,993,862 AOETYLENIC GLYCOLS AS CORROSION INHIBITORS Roger F. Monroe and Fred J. Lowes, Midland, Mich., and Gerald L. Foster and Billy 1).0akes, Tulsa, Okla., assignors to The Dow Chemical Company, Midland, Mich., a corporation of Delaware No Drawing. Filed Aug. 2, 1956, Ser. No. 601,641
6-Claims. (Cl. 252-146) This invention relates to corrosion inhibitors for use in aqueous hydrochloric acid to inhibit the corrosion of iron, steel, nickel or ferrous alloy metals exposed to said aqueous acid.
We have now discovered that certain acetylenic glycols, specifically, those having the formula R R Rd0E0-GE0d-R H H wherein R is a radical selected from the group consisting of H and CH are potent corrosion inhibitors and, as such, are particularly efiective in protecting iron, steel, [ferrous alloys and nickel from the corrosive attack of aqueous hydrochloric acid. By the term aqueous hydrochloric acid we mean HCl in the presence of a significant amount of Water and do not mean to exclude the presence of other substances.
According to the invention, the inhibitors are simply dissolved in the hydrochloric acid solution the corrosive action of which is to be inhibited. Only a small amount of inhibitor is required. As little as a few thousandths of .1 percent, based on the acid solution, significantly reduces the corrosion of iron and nickel exposed to the acid. The degree if inhibition increases with the concentration of the inhibitor up to a concentration of about 1 percent. Beyond this point there is little advantage in using more inhibitor.
The inhibitors of the invention are efiective not only at ordinary temperatures but also at elevated temperatures, up to the point at which the inhibitors decompose. They are effective in all concentrations of hydrochloric acid up to and including commercial concentrated acid (about 36 percent). Applications in which they are particularly useful include metal-cleaning baths, oil welltreating acids, boiler-cleaning solutions and the like.
In order to illustrate the effectiveness of our corrosion inhibitors we have conducted tests in which hydrochloric acid at various concentrations and containing 0.4 percent of the inhibitor being tested is placed in contact with a standard coupon of the metal to be protected. After 16 hr. the coupon is washed, dried and weighed to determine the amount of metal dissolved by the acid. From this is calculated the corrosion rate in terms of inches of penetration per year. Some typical results thus obtained are shown in Table I.
TABLE I Corrosion rates, inches penetration per year, of steel and nickel exposed to hydrochloric acid Results similar to those shown in Table I were obice Patented July 25, 1961 tained when other concentrations of hydrochloric acid, other temperatures in the range from room temperatures up to the decomposition point of the inhibitor, and other ferrous metals were used instead of those used in obtaining the data in Table I. It was also found that the effectiveness of the inhibitors was not impaired by the presence of liquids other than water, such as, for instance, alcohols, glycols or surfactants. Likewise, their efiectiveness was not impaired by the presence of various salts in the aqueous acid such as the soluble chlorides and sulfates.
We claim:
1. Aqueous hydrochloric acid containing about 5 to 36% concentration, by weight, and, as the sole active corrosion inhibitor therefor an efiective amount of a compound having the formula H H wherein R is a radical selected from the group consisting of H and --CH 2. A solution as in claim 1 wherein R is H.
3. A solution as in claim 1 wherein R is CH 4. A solution as in claim 1 wherein the concentration of the inhibitor is from a few thousandths percent to about one percent, by weight.
5; A process for inhibiting the corrosion of a metal of the group consisting of iron, steel, nickel and ferrous alloys by aqueous hydrochloric acid in contact therewith comprising maintaining in said acid a small but effective concentration of the inhibitor having the formula R RJJ- EC -CEO-ER H H wherein R is a radical selected from the group consisting of H and CH3.
6. A process as defined in claim 5 wherein the concentration of inhibitor is from a iew thousandths percent to about 1 percent, by weight.
References Cited in the tile of this patent UNITED STATES PATENTS 1,169,341 C-hrzesciuski et al Ian. 25, 19:16 1,841,768 Straus et a1. Ian. 19, 1932 1,963,934 Carothers et al June 19, 1934 2,152,406 Ducamp et al. Mar. 28, 1939 2,204,597 Humphreys et al June 18, .1940 2,250,445 Bruson et al July 29, 1941 2,355,599 Walker Aug. 8, 1944 2,371,644 Petering et al. Mar. 20, 1945 2,407,149 Gardenier Sept. 3, 1946 2,603,622 Berger et a1 July 15, 1952 2,726,269 Humphlett Dec. 6, 1955 2,775,624 Skeeters et al. Dec. 25, 1956 2,775,626 Schaaf et a1 Dec. 25, 1956 2,805,257 Lowes et al. Sept. 3, 1957 2,806,067 Monroe et al. Sept. .10, 1957 2,814,593 Beiswanger et a1 Nov. 26, 1957 2,838,458 Bachtel June 10, 1958 2,880,180 Foster et a1 Mar. 31, 1959 FOREIGN PATENTS 627,453 Great Britain Aug. 9, 1949 890,796 Germany Sept. 21, 1953 505,421 Belgium Sept. 15, 1951 1,075,385 France Apr. 14, 1954 1,079,916 France May 26, 1954 OTHER REFERENCES Corrosion Handbook by Uhlig, pp. 910912, pub. by John Wiley, N.Y., 1948.

Claims (1)

1. AQUEOUS HYDROCHLORIC ACID CONTAINING ABOUT 5 TO 36% CONCENTRATION, BY WEIGHT, AND, AS THE SOLE ACTIVE CORROSION INHIBITOR THEREFOR AN EFFECTIVE AMOUNT OF A COMPOUND HAVING THE FORMULA
US601641A 1956-08-02 1956-08-02 Acetylenic glycols as corrosion inhibitors Expired - Lifetime US2993862A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3125475A (en) * 1964-03-17 Method of producing a bright finish
US3282731A (en) * 1963-05-28 1966-11-01 United States Steel Corp Embrittlement-free pickling of ferrous metal
US4174269A (en) * 1978-06-21 1979-11-13 Ppg Industries, Inc. Method of treating electrodes
US4956076A (en) * 1989-09-28 1990-09-11 Betz Laboratories, Inc. Method of scavenging hydrogen halides from liquid hydrocarbonaceous mediums

Citations (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE505421A (en) *
US1169341A (en) * 1914-07-07 1916-01-25 Synthetic Patents Co Inc Alakali-metal acetones.
US1841768A (en) * 1927-11-24 1932-01-19 Winthrop Chem Co Inc Chlorinated and brominated ethine carbinols
US1963934A (en) * 1931-11-11 1934-06-19 Du Pont Vinylethinyl derivatives and processes for producing same
US2152406A (en) * 1935-12-10 1939-03-28 Ducamp Albert Jean Methods of pickling metals
US2204597A (en) * 1937-02-23 1940-06-18 Standard Oil Co Compounded lubricant
US2250445A (en) * 1938-10-01 1941-07-29 Rohm & Haas Process for producing acetylenic alcohols
US2355599A (en) * 1941-01-23 1944-08-08 Du Pont Acid metal treating baths
US2371644A (en) * 1942-10-01 1945-03-20 Westvaco Chlorine Products Cor Degreasing process
US2407149A (en) * 1944-09-08 1946-09-03 Edison Inc Thomas A Stabilized 2-chlor-butene-2
GB627453A (en) * 1947-07-16 1949-08-09 Glaxo Lab Ltd Improvements in and relating to the preparation of derivatives of cyclohexene
US2603622A (en) * 1948-10-01 1952-07-15 Berger Heinrich Halogen containing resin stabilized with an acetylene alcohol
DE890796C (en) * 1953-08-13 Badische Anilin- S. Soda-Fabrik Aktiengesellschaft, Ludwigshafen'Rhein Process for the production of diacetylene glycols
FR1075385A (en) * 1952-02-22 1954-10-15 Ciba Geigy Process for the preparation of new esters of carbamic acid and new products thus obtained
FR1079916A (en) * 1952-04-10 1954-12-03 Schering Ag Carbamic eters of acetylenic alcohols and their preparation
US2726269A (en) * 1955-12-06 Method of making acetylenic carbinols
US2775624A (en) * 1953-09-25 1956-12-25 Diamond Alkali Co Stabilized tetrachloroethylene
US2775626A (en) * 1953-11-04 1956-12-25 Nopco Chem Co Production of 1-ethynyl-2, 6, 6-trimethylcyclohex-1-ene
US2805257A (en) * 1956-08-02 1957-09-03 Dow Chemical Co 1-ethynyl-cyclohexylthiols
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
US2838458A (en) * 1955-09-30 1958-06-10 Dow Chemical Co Inhibited methyl chloroform
US2880180A (en) * 1956-09-10 1959-03-31 Dow Chemical Co Propargyl sulfide as a corrosion inhibitor in acidic solutions

Patent Citations (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE890796C (en) * 1953-08-13 Badische Anilin- S. Soda-Fabrik Aktiengesellschaft, Ludwigshafen'Rhein Process for the production of diacetylene glycols
BE505421A (en) *
US2726269A (en) * 1955-12-06 Method of making acetylenic carbinols
US1169341A (en) * 1914-07-07 1916-01-25 Synthetic Patents Co Inc Alakali-metal acetones.
US1841768A (en) * 1927-11-24 1932-01-19 Winthrop Chem Co Inc Chlorinated and brominated ethine carbinols
US1963934A (en) * 1931-11-11 1934-06-19 Du Pont Vinylethinyl derivatives and processes for producing same
US2152406A (en) * 1935-12-10 1939-03-28 Ducamp Albert Jean Methods of pickling metals
US2204597A (en) * 1937-02-23 1940-06-18 Standard Oil Co Compounded lubricant
US2250445A (en) * 1938-10-01 1941-07-29 Rohm & Haas Process for producing acetylenic alcohols
US2355599A (en) * 1941-01-23 1944-08-08 Du Pont Acid metal treating baths
US2371644A (en) * 1942-10-01 1945-03-20 Westvaco Chlorine Products Cor Degreasing process
US2407149A (en) * 1944-09-08 1946-09-03 Edison Inc Thomas A Stabilized 2-chlor-butene-2
GB627453A (en) * 1947-07-16 1949-08-09 Glaxo Lab Ltd Improvements in and relating to the preparation of derivatives of cyclohexene
US2603622A (en) * 1948-10-01 1952-07-15 Berger Heinrich Halogen containing resin stabilized with an acetylene alcohol
FR1075385A (en) * 1952-02-22 1954-10-15 Ciba Geigy Process for the preparation of new esters of carbamic acid and new products thus obtained
FR1079916A (en) * 1952-04-10 1954-12-03 Schering Ag Carbamic eters of acetylenic alcohols and their preparation
US2775624A (en) * 1953-09-25 1956-12-25 Diamond Alkali Co Stabilized tetrachloroethylene
US2775626A (en) * 1953-11-04 1956-12-25 Nopco Chem Co Production of 1-ethynyl-2, 6, 6-trimethylcyclohex-1-ene
US2814593A (en) * 1953-12-18 1957-11-26 Gen Aniline & Film Corp Corrosion inhibition
US2838458A (en) * 1955-09-30 1958-06-10 Dow Chemical Co Inhibited methyl chloroform
US2805257A (en) * 1956-08-02 1957-09-03 Dow Chemical Co 1-ethynyl-cyclohexylthiols
US2806067A (en) * 1956-08-02 1957-09-10 Dow Chemical Co Alpha-ethynyl-2, 4, 6-trimethyl-3-cyclohexene-1-methanol
US2880180A (en) * 1956-09-10 1959-03-31 Dow Chemical Co Propargyl sulfide as a corrosion inhibitor in acidic solutions

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3125475A (en) * 1964-03-17 Method of producing a bright finish
US3282731A (en) * 1963-05-28 1966-11-01 United States Steel Corp Embrittlement-free pickling of ferrous metal
US4174269A (en) * 1978-06-21 1979-11-13 Ppg Industries, Inc. Method of treating electrodes
US4956076A (en) * 1989-09-28 1990-09-11 Betz Laboratories, Inc. Method of scavenging hydrogen halides from liquid hydrocarbonaceous mediums

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