US3868217A - Corrosion inhibition - Google Patents

Corrosion inhibition Download PDF

Info

Publication number
US3868217A
US3868217A US46834774A US3868217A US 3868217 A US3868217 A US 3868217A US 46834774 A US46834774 A US 46834774A US 3868217 A US3868217 A US 3868217A
Authority
US
Grant status
Grant
Patent type
Prior art keywords
corrosion
water
system
mg
acid
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
Inventor
William Robert Hollingshad
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.)
Calgon Corp
Original Assignee
Calgon Corp
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
Grant date

Links

Images

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
    • 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
    • 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
    • C23F11/167Phosphorus-containing compounds

Abstract

Use of mono-, di-, and triphosphoric acid esters of triethanol amine and mixtures thereof to inhibit the corrosion of metals by oxygen-bearing waters.

Description

United States Patent 1 [111 3,868,217 Hollingshad Feb. 25, 1975 CORROSION INHIBITION [56] References Cited [75] Inventor: William Robert Hollingshad, Bethe] UNITED STATES PATENTS Park, Pa. 2,737,498 3/1956 Frasch 252/389 [73] Assignee: Calgon Corporation, Robinson Townshi Pa.

3,422,166 1/1969 22 i May 9 1974 3,787,319 1/1974 Larsen 21/27 A [21] Appl 468347 Primary Examiner-Barry S. Richman Related US, A li ti D t Assistant Examiner-Da1e Loverchleck [63] Continuation-impart of Ser. No. 347,009, April 2, Attorney Agent or Flrm Mamn Katz; Harry 1973, abandoned. Wesflake [52] 11.8. C1. 2l/2.7 A, 21/27 R, 252/389 A, [57] ABSTRACT 252/392! 252/394 Use of mono-, di-, and triphosphoric acid esters of tri- [5 1] Int. Cl. C23f 11/14, C23f 11/16 ethanol amine and mixtures thereof to inhibit the Cop [58] Field of Search 21/27 A, 2.5 A; 252/148, rosion of metals by oxygembearing waters 4 Claims, No Drawings CORROSION INHIBITION This application is a continuation-in-part of U.S. Ser. No. 347,009, filed Apr. 2, 1973 and now abandoned.

This invention relates to the use of the mono-, di-, and triphosphoric acid esters of triethanol amine N(CH CH O(PO where n=l-3 and mixtures thereof, alone or in combination with certain triazoles. thiazoles and mixtures thereof, for inhibiting corrosion of metals by oxygen-bearing waters.

Oxygen corrosion is, of course, a serious problem in any metal-containing water system. The corrosion of iron and steel is of principal concern because of their extensive use in many types of industrial and municipal water systems. Copper and its alloys, aluminum and its alloys, and galvanized steel are also used in water sys tems and are subject to corrosion. The use of similar corrosion inhibitors is disclosed in U.S. Pat. No. 3,260,673 to Fisher, and No. 3,397,150 to Burt, et al., and No. 3,422,166 to Pitman.

l have found that the mono-, di-, and triphosphoric acid esters of triethanol amine and mixtures thereof are effective corrosion inhibitors without the necessity of adding zinc, chromates or other additives. These esters effectively inhibit the corrosion of metals in water systems when they are added in amounts of from about 10 to 100 mg/l either alone or in combination with from about 1 to 10 mg/l of an effective triazole or thiazole, as for example, mercaptobenzothiazole or benzotriaz ole.

The following table shows the results of experiments which demonstrate the effectiveness ofa mixture of the mono-, di, and triphosphoric acid ester of triethanol amine and the water-soluble salts thereof in inhibiting metallic corrosion. These tests were run in synthetic Pittsburgh water. Steel electrodes were used in polarization test cells with the initial pH at 7.0. Inhibitor concentrations were calculated on the basis of active material. The amount of corrosion that had taken place was determined from the current density at the intersection of an extrapolation of the so-called Tafel portion of the anodic polarization curve with the equilibrium or mixed potential value, usually referred to as the corrosion potential. E Application of Faraday's Lay allows a computation of a direct mathematical relationship between the current density of E,.,,,.,., expressed in amperes per square centimeter and a more useful corrosion rate expression such as milligrams of steel consumed per square decimeter of surface per day (m.d.d.) and mils per year (m.p.y.). This relationship is such that a current density value of 4.0 l0' amperes/cm 1.0 mg/dm /day. Further, the m.p.y. value is calculated from the usual formula: m.p.y. m.d.d. (1.44/density, using a density value of 7.87 g/cm for The following test provided corrosion rate data under field conditions. Pilot plant size cooling tower-heat exchanger test equipment (CTHE) was used to simulate large industrial recirculated cooling water systems. The makeup water for this experiment was a synthetically prepared tap water similar in analysis to Pittsburgh, Pennsylvania tap water. The pH of the water in the operating system was controlled to 7.0 t 0.1 by feeding a dilute solution of sulfuric acid on demand from an automatic pH control system. This simulation also included flow velocities of 2 5 ft./'sec., natural concentration of the minerals in the water to about five times their concentration in the makeup water (5X) by evaporation, several different metals exposed (but not galvanically coupled), three successive heat transfer surfaces, etc. This system is highly instrumented and prov vides substantial data relating to the performance of in hibitors since one can evaluate not only test coupons, but also steel and admiralty brass heat transfer surfaces, and continuously record instrumental corrosion rate data (Corrater instrument, Magna Corp., Santa Fe Springs, Calif). The aforenoted mixture of phosphate ester of triethanol amine was maintained at 30 60 mg/l during this test.

Corrosion rates on steel during this 3M2 week long test (the test ran continuously, 24 hrs/day, for twentyfour consecutive days) were 1.5 to 3.5 m.p.y. on test coupons; the recording Corrater chart showed a very stable value of 1.5 i 0.5 m.p.y. The heat transfer surfaces of the heat exchanger tubes were clean and essentially free of any corrosive attack.

The copper alloy specimens initially showed corrosion rates of 0.5 0.9 m.p.y. Since this is a bit high for copper alloys, 1 2 mg/l of a specific copper corrosion inhibitor, sodium mercaptobenzothiazole was fed to the system. This reduced the copper alloy corrosion rates to an acceptable rate of less than 0.1 m.p.y. Benzotriazole would be equally effective in this application. Both products are compatible with the ester and can be used interchangeably in a commercial preparation.

1 claim:

1. A method of inhibiting the corrosion of metals in a water system which comprise-s maintaining in the water of said system at least about 10 mg/l of a phosphoric acid ester of triethanol amine.

2. A method as in claim 1 which further comprises maintaining in said system at least about 1 mg/l of a member selected from the group consisting of thiazoles and triazoles.

3. A method as in claim 2 wherein the thiazole is mercaptobenzothiazole.

4. A method as in claim 2 wherein the triazole is ben-

Claims (4)

1. A METHOD OF INHIBITING THE CORROSION OF METALS IN A WATER SYSTEM WHICH COMPRISES MAINTAINING IN THE WATER OF SAID SYSTEM AT LEAST ABOUT 100 MG/L OF A PHOSPHORIC ACID ESTER OF TRIETHANOL AMINE.
2. A method as in claim 1 which further comprises maintaining in said system at least about 1 mg/l of a member selected from the group consisting of thiazoles and triazoles.
3. A method as in claim 2 wherein the thiazole is mercaptobenzothiazole.
4. A method as in claim 2 wherein the triazole is benzotriazole.
US3868217A 1973-04-02 1974-05-09 Corrosion inhibition Expired - Lifetime US3868217A (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US34700973 true 1973-04-02 1973-04-02
US3868217A US3868217A (en) 1973-04-02 1974-05-09 Corrosion inhibition

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US3868217A US3868217A (en) 1973-04-02 1974-05-09 Corrosion inhibition

Publications (1)

Publication Number Publication Date
US3868217A true US3868217A (en) 1975-02-25

Family

ID=26995088

Family Applications (1)

Application Number Title Priority Date Filing Date
US3868217A Expired - Lifetime US3868217A (en) 1973-04-02 1974-05-09 Corrosion inhibition

Country Status (1)

Country Link
US (1) US3868217A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4120655A (en) * 1976-07-13 1978-10-17 Societe Nationale Elf Aquitaine Method for the inhibition of corrosion of ferrous metals in an aqueous medium
DE3526640A1 (en) * 1985-07-25 1987-01-29 Benckiser Knapsack Gmbh Corrosion and stone protection products for domestic water systems
US4804685A (en) * 1984-10-12 1989-02-14 Surgikos, Inc. Buffered glutaraldehyde sterilizing and disinfecting compositions
US5994211A (en) * 1997-11-21 1999-11-30 Lsi Logic Corporation Method and composition for reducing gate oxide damage during RF sputter clean
US6068879A (en) * 1997-08-26 2000-05-30 Lsi Logic Corporation Use of corrosion inhibiting compounds to inhibit corrosion of metal plugs in chemical-mechanical polishing
US6117795A (en) * 1998-02-12 2000-09-12 Lsi Logic Corporation Use of corrosion inhibiting compounds in post-etch cleaning processes of an integrated circuit
WO2006096477A1 (en) * 2005-03-04 2006-09-14 The Procter & Gamble Company Automatic dishwashing composition with corrosion inhibitors
US8434631B2 (en) 2003-12-02 2013-05-07 Alfred Knox Harpole Rackable collapsible stackable unit

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2737498A (en) * 1946-07-12 1956-03-06 Produits Chim Terres Rares Soc Product for and process of treating metallic articles before coating
US3260673A (en) * 1964-01-27 1966-07-12 Monsanto Co Corrosion inhibited phosphoric acid composition
US3397150A (en) * 1966-03-15 1968-08-13 Du Pont Composition and method for treating surfaces
US3422166A (en) * 1964-03-20 1969-01-14 Mobil Oil Corp Triethanolamine salts of mono- and dinonyl phenol (ethoxylate) phosphate acid esters
US3787319A (en) * 1969-04-02 1974-01-22 Marathon Oil Co Amine/phosphate composition useful as corrosion and scale inhibitor

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2737498A (en) * 1946-07-12 1956-03-06 Produits Chim Terres Rares Soc Product for and process of treating metallic articles before coating
US3260673A (en) * 1964-01-27 1966-07-12 Monsanto Co Corrosion inhibited phosphoric acid composition
US3422166A (en) * 1964-03-20 1969-01-14 Mobil Oil Corp Triethanolamine salts of mono- and dinonyl phenol (ethoxylate) phosphate acid esters
US3397150A (en) * 1966-03-15 1968-08-13 Du Pont Composition and method for treating surfaces
US3787319A (en) * 1969-04-02 1974-01-22 Marathon Oil Co Amine/phosphate composition useful as corrosion and scale inhibitor

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4120655A (en) * 1976-07-13 1978-10-17 Societe Nationale Elf Aquitaine Method for the inhibition of corrosion of ferrous metals in an aqueous medium
US4804685A (en) * 1984-10-12 1989-02-14 Surgikos, Inc. Buffered glutaraldehyde sterilizing and disinfecting compositions
DE3526640A1 (en) * 1985-07-25 1987-01-29 Benckiser Knapsack Gmbh Corrosion and stone protection products for domestic water systems
US6068879A (en) * 1997-08-26 2000-05-30 Lsi Logic Corporation Use of corrosion inhibiting compounds to inhibit corrosion of metal plugs in chemical-mechanical polishing
US6383414B1 (en) 1997-08-26 2002-05-07 Lsi Logic Corporation Use of corrosion inhibiting compounds to inhibit corrosion of metal plugs in chemical-mechanical polishing
US5994211A (en) * 1997-11-21 1999-11-30 Lsi Logic Corporation Method and composition for reducing gate oxide damage during RF sputter clean
US6204550B1 (en) 1997-11-21 2001-03-20 Lsi Logic Corporation Method and composition for reducing gate oxide damage during RF sputter clean
US6117795A (en) * 1998-02-12 2000-09-12 Lsi Logic Corporation Use of corrosion inhibiting compounds in post-etch cleaning processes of an integrated circuit
US8434631B2 (en) 2003-12-02 2013-05-07 Alfred Knox Harpole Rackable collapsible stackable unit
WO2006096477A1 (en) * 2005-03-04 2006-09-14 The Procter & Gamble Company Automatic dishwashing composition with corrosion inhibitors

Similar Documents

Publication Publication Date Title
US3589859A (en) Gluconate salt inhibitors
US3532639A (en) Corrosion inhibiting with combinations of zinc salts,and derivatives of methanol phosphonic acid
Wilde A critical appraisal of some popular laboratory electrochemical tests for predicting the localized corrosion resistance of stainless alloys in sea water
LeChevallier et al. Examining the relationship between iron corrosion and the disinfection of biofilm bacteria
US4351796A (en) Method for scale control
Zucchi et al. The influence of the chromium content on the inhibitive efficiency of some organic compounds
US5575920A (en) Method of inhibiting scale and controlling corrosion in cooling water systems
US3714066A (en) Methods of inhibiting corrosion with ethane diphosphonate compositions
Larson et al. Laboratory studies relating mineral quality of water to corrosion of steel and cast iron
US4406811A (en) Composition and method for controlling corrosion in aqueous systems
US4659481A (en) Water treatment polymers and methods of use thereof
US3803047A (en) Organic phosphonic acid compound corrosion protection in aqueous systems
US4649025A (en) Anti-corrosion composition
US3699052A (en) Corrosion inhibitor composition containing a glycine,chelating agent,phosphoric or boric acid ester,and a water soluble divalent metal salt
US5611991A (en) Corrosion inhibitor containing phosphate groups
US4066398A (en) Corrosion inhibition
Sekine et al. Effect of 1-hydroxyethylidene-1, 1-diphosphonic acid on the corrosion of SS 41 steel in 0.3% sodium chloride solution
US4237090A (en) Method for inhibiting corrosion in aqueous systems
US4443340A (en) Control of iron induced fouling in water systems
US4026815A (en) Method for preventing corrosion in water-carrying systems
US4101441A (en) Composition and method of inhibiting corrosion
US4675158A (en) Mercaptobenzothiazole and tolyltriazole corrosion inhibiting compositions
US4895663A (en) Water treatment polymers and methods of use thereof
US4409121A (en) Corrosion inhibitors
US3890228A (en) Polyacrylate-polyphosphonic acid treatment in aqueous systems

Legal Events

Date Code Title Description
AS Assignment

Owner name: CALGON CORPORATION ROUTE 60 & CAMPBELL S RUN ROAD,

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST. EFFECTIVE JULY 1, 1982;ASSIGNOR:CALGON CARBON CORPORATION (FORMERLY CALGON CORPORATION) A DE COR.;REEL/FRAME:004076/0929

Effective date: 19821214