US3819527A - Composition and method for inhibiting acid attack of metals - Google Patents

Composition and method for inhibiting acid attack of metals Download PDF

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Publication number
US3819527A
US3819527A US00303956A US30395672A US3819527A US 3819527 A US3819527 A US 3819527A US 00303956 A US00303956 A US 00303956A US 30395672 A US30395672 A US 30395672A US 3819527 A US3819527 A US 3819527A
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United States
Prior art keywords
percent
acid
composition
thiourea
attack
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US00303956A
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English (en)
Inventor
E Hayman
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Henkel Corp
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Amchem Products Inc
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Publication date
Application filed by Amchem Products Inc filed Critical Amchem Products Inc
Priority to US00303956A priority Critical patent/US3819527A/en
Priority to CA183,301A priority patent/CA1024733A/en
Priority to AU61424/73A priority patent/AU469688B2/en
Priority to JP12157673A priority patent/JPS5321365B2/ja
Priority to IT70232/73A priority patent/IT999721B/it
Priority to DE2355436A priority patent/DE2355436C3/de
Priority to FR7339365A priority patent/FR2205563B1/fr
Priority to GB5145373A priority patent/GB1416079A/en
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Publication of US3819527A publication Critical patent/US3819527A/en
Assigned to AMCHEM PRODUCTS, INC. A CORP. OF DEL. reassignment AMCHEM PRODUCTS, INC. A CORP. OF DEL. MERGER (SEE DOCUMENT FOR DETAILS). Assignors: AMCHEM PRODUCTS, INC. (MERGED INTO), HHC, INC. (CHANGED TO)
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Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C23F11/04—Inhibiting 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
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
    • C23G1/06—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors

Definitions

  • ABSTRACT A composition comprising a cycliic trimer of methylene ortho-toluidine, thiourea, and a sulfonium salt for use in an acidic aqueous composition for the purpose of inhibiting acid attack on metallic surfaces which are contacted with the acidic composition.
  • This invention relates to reducing the attack of acid on metals which are contacted with an acidic aqueous composition. More particularly, this inventionv relates to a composition and its use in an acidic aqueous solution for the purpose of inhibiting or reducing the tendency of acid attack of metallic surfaces which are subjected to the acidic aqueous solution.
  • inhibitory compositions to the acid composition for the purpose of inhibiting acid attack on the metallic surfaces that are contacted with the acidic composition.
  • the inhibitory composition functions to reduce or prevent the tendency of the acid to corrode, degrade or otherwise attack the metallic surface without adversely affecting the desired properties of the acidic composition.
  • Materials which so function generally are referred to as acid inhibitors.
  • This invention relates to an acid inhibitor composition and to its use.
  • Acid inhibitors disclosed in the aforementioned patents include nitrogencontaining compounds, triphenyl sulfonium chloride, and acetylenic alcohols. These acid inhibitors are a few examples of the many that are known. Some examples of other known inhibitors are arsenic compounds, thioureas, heterocylic compounds containing sulfur and/or nitrogen, such as mercapto benzothiazole and Schiffs bases, and aldehydes, such as formaldehyde and benzaldehyde. Mixtures of such acid inhibitors have been used also.
  • the present invention is directed to the provision of an acid inhibitor that can be prepared readily from relatively low cost ingredients that are readily available, and an acid inhibitor that has excellent acid inhibiting properties.
  • An additional objective of this invention is to provide an improved process for reducing acid attack on metallic surfaces by acidic compositions which come into contact therewith.
  • composition comprising a cyclic trimer of methylene orthotoluidine, thiourea, and a sulfonium salt which 5 composition can be used in an acidic aqueous composition for the purpose of inhibiting acid attack on metallic surfaces which are contacted therewith.
  • the acid inhibitor composition of this invention can be used in any application in which it is desired to prevent acid attack of metals.
  • the acid inhibitor composition of this invention comprises an aqueous solution containing the following ingredients in the amounts indicated.
  • cyclic trimer of methylene orthotoluidine 30-60 40-50 thiourea l-l5 l-S sulfonium salt (1.5-25 1-5
  • the cyclic trimer of methylene ortho-toluidine is prepared by reacting formaldehyde and o-toluidine to form a Schiffs base, namely, methylene o-toluidine.
  • the third essential component of the inhibiting composition of this invention is a sulfonium salt of the formula wherein R, R and R are each hydrocarbon radicals, such as for example, those selected from the group consisting of alkyl, aryl and aralkyl and wherein X is an acid anion, preferably an anion of a strong mineral acid.
  • R, R and R are each hydrocarbon radicals, such as for example, those selected from the group consisting of alkyl, aryl and aralkyl and wherein X is an acid anion, preferably an anion of a strong mineral acid.
  • Formula 2 above includes within its scope compounds wherein said R', R and R radicals are the same radicals or are different radicals.
  • Formula 2 above includes also compounds wherein one or more of the said Rl, R and R radicals contain one or more of the same or different substituents, examples of which include hydroxy, halo and alkyl groups.
  • radicals R, R and R of Formula 2 above are propyl, nonyl, dodecyl, isobutyl, phenyl, hydroxy-phenyl, dodecyl phenyl, benzyl and 4-hydroxy- 3,5-dimethylphenyl. It is preferred that at least one of the aforesaid R, R and R radicals be aryl or aralkyl and most preferably, each of said radicals is aryl, such as for example phenyl or p-chlorophenyl.
  • Examples of X, the acid anion, in Formula 2 above, are chloride, bromide, iodide and sulfate, the first mentioned being preferred.
  • Sulfonium salts and methods for their preparation are known. For example, they can be prepared by the reaction of an aromatic hydrocarbon with a sulfur monohalide in the presence of anhydrous aluminum chloride and a halogen.
  • Triphenyl sulfonium chloride is the preferred sulfonium salt for use in this invention.
  • additives be combined with the aforementioned essential ingredients in order to increase the overall effectiveness of the inhibiting composition.
  • additives include materials which function as foaming agents and which increase the solubility of one or more of the essential ingredients of the composition.
  • these additives are surface active agents and solvents for the components comprising the composition. Any surface active agent compatible with the other components of the composition can be used including cationic and nonionic surface active agents with the last mentioned being preferred.
  • non-ionic surface active agents such as ethoxylated secondary alcohols and ethoxylated nonyl phenols and related compounds, such as thiols, and polar solvents such as alcohols, for example the lower alcohols, such as methanol and isopropanol.
  • Additives such as those described above, have been used previously with acid inhibitors and the amounts employed in the'composition of this invention can be determined readily from past experience. In general, the total amount of additives present in the composition should be no more than about percent.
  • the composition is added to the particular acidic composition utilized in an amount effective to inhibit the attack of the acid on the metal which is exposed to the acid.
  • the amount of inhibiting Formula 2 composition that will be effective to the extent desired will vary depending on a number of conditions. Such conditions include the particular components and amounts comprising the inhibiting composition, the particular acidic composition (including concentration) that is utilized, the type of metal cleaning operation or acidizing operation that is being performed and also the particular metal which is being subjected to said operations.
  • the inhibiting composition of this invention can be used, it will be appreciated that the most effective amount should be determined from experience gained in using the composition in a particular application. For guidance purposes, it is noted that it has been observed that generally good results can be obtained by adding the inhibiting composition to an acidic composition in an amount such that the inhibiting composition comprises from about 0.01 percent to about 5 percent by weight of the total weight of the inhibitor-containing acid composition and preferably from about 0.025 percent to about 1 percent by weight.
  • the desired inhibiting effect is not as apparent. If more than about 5 percent of the inhibiting composition is employed, the inhibiting properties seem to increase very slightly over that observable when the inhibiting composition comprises about 4.5 percent to about 5 percent. Indeed, it has been ob-. served that about 1 percent of the inhibiting composition gives maximum inhibition in many applications.
  • the inhibitor composition of this invention can be employed in any application where, for example, it is desired to inhibit the attack of an acid on metals, including particularly metal cleaning operations.
  • the inhibiting composition of this invention can be utilized with hydrochloric acid or other of the metal cleaning or pickling acids the so-called non-oxidizing acids. Included in this category are inorganic acids such as phosphoric, sulfamic and sulfuric and organic acids such as acetic, citric, formic, glycolic and oxalic.
  • the acid inhibitor of the present invention performs particularly well in sulfuric acid pickling solutions.
  • the acid inhibitor can also be utilized to protect from acid attack other metals such as for example, copper, brass, bronze and other alloys such as stainless steel.
  • the acid inhibitors of the present invention have excellent stability in acidic aqueous compositions.
  • the acid inhibitors can be prepared readily and exhibit excellent acid inhibiting properties.
  • An aqueous solution consisting essentially of, in weight percent based on the total weight of the solution:
  • thiourea compound selected from the group consisting of thiourea and substituted thiourea having alkyl groups of from one to about four carbon atoms;
  • R. R and R are hydrocarbon radicals selected from the group consisting of alkyl, aryl and aralkyl and wherein X is an acid anion.
  • a solution according to claim 1 wherein said thiourea compound is NH CS-NH and wherein said sulfonium salt is triphenyl sulfonium chloride.
  • a solution accordingto claim 2 wherein said thiourea compound is NH -CSNH and wherein said sulfonium salt is triphenyl sulfonium chloride.
  • a solution according to claim 2 wherein said thiourea compound is diethyl thiourea and said sulfonium salt is triphenyl sulfonium chloride.
  • a method for inhibiting acid attack of metallic surfaces comprising contacting a metallic surface with an acidic aqueous composition comprising a non-oxidizing acid of the type that tends to attack metals which are contacted therewith and, in acid inhibiting amounts, an inhibitor composition consisting essentially of about 30 to about wt. percent of a cyclic trimer of methylene ortho-toluidine, about 1 to about 15 wt. percent of a thiourea compound selected from the group consisting of thiourea and substituted thioureas having alkyl groups of from one to about four carbon atoms, and about 1 to about 25 wt. percent of a sulfonium salt having the formula:
  • R, R and R are hydrocarbon radicals selected from the group consisting of alkyl, aryl and aral kyl and wherein X is an acid anion.
  • said inhibitor composition consists essentially of about 40 to about 50 wt. percent ofa cyclic trimer of methylene ortho-toluidine, about 1 to about 5 wt. percent of thiourea and about 1 to about 5 wt. percent of triphenyl sulfonium chloride.
  • said inhibitor composition consists essentially of about 40 to about 50 wt. percent of a cyclic trimer of methylene ortho-toluidine, about 1 to about 5 wt. percent of diethyl thiourea and about 1 to about 5 wt. percent of triphenyl sulfonium chloride.
  • a method according to claim 9 wherein said acid is sulfuric acid.
  • said inhibitor composition consists essentially of about 40 to about 50 wt. percent of said cyclic trimer of methylene orthotoluidine, about 1 to about 5 wt. percent of said thiourea compound, and about 1 to about 5 wt. percent of said sulfonium salt.
  • a method according to claim 12 wherein said acid is sulfuric acid.
  • An acidic aqueous solution containing a nonoxidizing acid of the type that tends to attack metallic said aqueous solution is present in an amount of about 0.025 to about 1 percent by weight of the composition.
  • composition according to claim 15 wherein said acid is sulfuric acid.
  • composition according to claim 16 wherein said acid is sulfuric acid.

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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)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
US00303956A 1972-11-06 1972-11-06 Composition and method for inhibiting acid attack of metals Expired - Lifetime US3819527A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
US00303956A US3819527A (en) 1972-11-06 1972-11-06 Composition and method for inhibiting acid attack of metals
CA183,301A CA1024733A (en) 1972-11-06 1973-10-12 Composition and method for inhibiting acid attack of metals
AU61424/73A AU469688B2 (en) 1972-11-06 1973-10-16 Composition and method foe inhibiting acid attack of metals
JP12157673A JPS5321365B2 (OSRAM) 1972-11-06 1973-10-29
IT70232/73A IT999721B (it) 1972-11-06 1973-11-05 Composizione e procedimento per inibire l attacco di acidi su metalli
DE2355436A DE2355436C3 (de) 1972-11-06 1973-11-06 Mittel zur Verhinderung eines Angreifens von Säuren auf Metalle auf Grundlage eines eine Thioharnstoffverbindung und ein Sulfoniumsalz enthaltenden Inhibitorengemisches
FR7339365A FR2205563B1 (OSRAM) 1972-11-06 1973-11-06
GB5145373A GB1416079A (en) 1972-11-06 1973-11-06 Composition for inhibiting the attach of acids on metals

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US00303956A US3819527A (en) 1972-11-06 1972-11-06 Composition and method for inhibiting acid attack of metals

Publications (1)

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US3819527A true US3819527A (en) 1974-06-25

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US00303956A Expired - Lifetime US3819527A (en) 1972-11-06 1972-11-06 Composition and method for inhibiting acid attack of metals

Country Status (8)

Country Link
US (1) US3819527A (OSRAM)
JP (1) JPS5321365B2 (OSRAM)
AU (1) AU469688B2 (OSRAM)
CA (1) CA1024733A (OSRAM)
DE (1) DE2355436C3 (OSRAM)
FR (1) FR2205563B1 (OSRAM)
GB (1) GB1416079A (OSRAM)
IT (1) IT999721B (OSRAM)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4180469A (en) * 1977-12-30 1979-12-25 Amchem Products, Inc. Dithiocarbamate sulfonium salt inhibitor composition
US4637899A (en) * 1984-01-30 1987-01-20 Dowell Schlumberger Incorporated Corrosion inhibitors for cleaning solutions
US4830827A (en) * 1984-04-23 1989-05-16 The Dow Chemical Company Method of inhibiting corrosion using perhydro-s-triazine derivatives
US20090032057A1 (en) * 2007-02-01 2009-02-05 Henkel Corporation Acid inhibitor compositions for metal cleaning and/or pickling
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

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2965334D1 (en) * 1979-01-03 1983-06-16 Amchem Prod Dithiocarbamate/sulfonium salt corrosion inhibitor composition and its use in acidic cleaning solutions
US5582934A (en) * 1995-05-17 1996-12-10 Henkel Corporation Additives for electrolytic solutions

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1719649A (en) * 1927-01-11 1929-07-02 Vanderbilt Co R T Pickling and cleaning of metal
US2049517A (en) * 1934-06-06 1936-08-04 American Chem Paint Co Method of and material for inhibiting or retarding acid corrosion of ferrous metals
US2941949A (en) * 1957-05-14 1960-06-21 Amchem Prod Acid baths for cleaning and pickling metal
US2959555A (en) * 1956-09-28 1960-11-08 Dow Chemical Co Copper and iron containing scale removal from ferrous metal
US3668137A (en) * 1969-04-01 1972-06-06 Amchem Prod Composition and method for inhibiting acid attack of metals

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1608622A (en) * 1925-09-30 1926-11-30 Newport Co Process for preventing the dissolution of iron and steel in sulphuric acid and pickling baths
US2889277A (en) * 1955-11-16 1959-06-02 Cities Service Res & Dev Co Method of inhibiting corrosion of metals

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1719649A (en) * 1927-01-11 1929-07-02 Vanderbilt Co R T Pickling and cleaning of metal
US2049517A (en) * 1934-06-06 1936-08-04 American Chem Paint Co Method of and material for inhibiting or retarding acid corrosion of ferrous metals
US2959555A (en) * 1956-09-28 1960-11-08 Dow Chemical Co Copper and iron containing scale removal from ferrous metal
US2941949A (en) * 1957-05-14 1960-06-21 Amchem Prod Acid baths for cleaning and pickling metal
US3668137A (en) * 1969-04-01 1972-06-06 Amchem Prod Composition and method for inhibiting acid attack of metals

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4180469A (en) * 1977-12-30 1979-12-25 Amchem Products, Inc. Dithiocarbamate sulfonium salt inhibitor composition
US4637899A (en) * 1984-01-30 1987-01-20 Dowell Schlumberger Incorporated Corrosion inhibitors for cleaning solutions
US4830827A (en) * 1984-04-23 1989-05-16 The Dow Chemical Company Method of inhibiting corrosion using perhydro-s-triazine derivatives
US20090032057A1 (en) * 2007-02-01 2009-02-05 Henkel Corporation Acid inhibitor compositions for metal cleaning and/or pickling
US8278258B2 (en) 2007-02-01 2012-10-02 Henkel Ag & Co. Kgaa Acid inhibitor compositions for metal cleaning and/or pickling
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

Also Published As

Publication number Publication date
AU469688B2 (en) 1976-02-19
JPS4977844A (OSRAM) 1974-07-26
CA1024733A (en) 1978-01-24
DE2355436C3 (de) 1978-10-26
IT999721B (it) 1976-03-10
AU6142473A (en) 1975-04-17
FR2205563B1 (OSRAM) 1977-08-05
DE2355436A1 (de) 1974-05-22
FR2205563A1 (OSRAM) 1974-05-31
JPS5321365B2 (OSRAM) 1978-07-03
DE2355436B2 (de) 1978-03-02
GB1416079A (en) 1975-12-03

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Legal Events

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AS Assignment

Owner name: AMCHEM PRODUCTS, INC. A CORP. OF DEL.

Free format text: MERGER;ASSIGNORS:AMCHEM PRODUCTS, INC. (MERGED INTO);HHC, INC. (CHANGED TO);REEL/FRAME:004102/0461

Effective date: 19810320