US3803048A - Organic phosphonic acid compound corrosion protection in aqueous systems - Google Patents
Organic phosphonic acid compound corrosion protection in aqueous systems Download PDFInfo
- Publication number
- US3803048A US3803048A US00300938A US30093872A US3803048A US 3803048 A US3803048 A US 3803048A US 00300938 A US00300938 A US 00300938A US 30093872 A US30093872 A US 30093872A US 3803048 A US3803048 A US 3803048A
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- US
- United States
- Prior art keywords
- acid
- aqueous systems
- water
- zinc
- aqueous
- 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
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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
- 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
- C23G1/066—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors organic inhibitors phosphorus-containing compounds
-
- 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
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
-
- Y—GENERAL 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S507/00—Earth boring, well treating, and oil field chemistry
- Y10S507/939—Corrosion inhibitor
Definitions
- the invention disclosed relates to organo-phosphonic acid compounds in combination with zinc salts for use to inhibit metal corrosion in aqueous systems.
- the organophosphonic acid compounds include alkylene polyphosphonic acids, and the water-soluble salts and esters thereof.
- the method of this invention for preventing corrosion of metals in contact with an aqueous liquid comprises maintaining in the aqueous liquid from 1 to 10,000 ppm. of the alkylene polyphosphonic acid, salts or esters thereof, and from 1 to 10,000 ppm. of a water-soluble zinc salt.
- Water-soluble inorganic chromates are widely used to treat industrial water systems to prevent corrosion of metal parts in contact therewith. When these chromates are employed alone, they are used in concentrations as low as 200 ppm. and as high as 10,000 ppm., depending upon the protection needed and the permissible cost. When these chromates are used in combinations with molecularly dehydrated inorganic phosphates such as disclosed in U.S. Pat. No. 2,711,391, chromate concentrations as low as ppm. have been found adequate in mild corrosive systems. Therefore, combinations of chromates and molecularly dehydrated phosphates are widely used.
- chromates are highly effective corrosion inhibitors, their use is subject to several difficulties. Chromates cause serious skin and eye irritations, and chromates cannot be used in aqueous systems such as cooling towers or air-wash units where .the. resulting spray will contact people. Chromate solutions, because they are toxic, often require chemical treatment before being discharged to waste systems. Furthermore, chromates degrade organic compounds mixed therewith, limiting the types or organic compounds which can be mixed with the chromates in dry mixtures and aqueous solutions.
- the composition contains an organic phosphonic acid compound in combination with a water-soluble zinc salt.
- compositions of this invention are useful for treating a variety of aqueous systems, that is, any aqueous system corrosive to metal surfaces in contact therewith.
- Suitable systems which can be treated according to this invention include water treatment systems, cooling towers, water circulating systems, and the like wherein fresh water, brines, sea water, sewage effluents, industrial waste waters, and the like are circulated in contact with metal surfaces.
- These compounds are useful in acid pickling baths, radiator coolers, hydraulic liquids, antifreezes, heat transfer mediums, and petroleum well treatments.
- the process of this invention is suitable for reducing the corrosion of iron, copper, aluminum, zinc and alloys containing these metals such as steel and other ferrous alloys, brass, and the like which are in contact with corrosive aqueous systems.
- compositions of this invention contain from 1 to percent of an organo-phosphonic acid compound.
- the preferred organo-phosphonic acid compound for use in the composition of this invention is an alkylene diphosphonic acid having the foregoing Formula A, such as those disclosed in U.S. Pat. Nos. 3,214,454 and 3,297,578, the entire disclosures of which are incorporated herein by reference.
- an alkylene diphosphonic acid having the foregoing Formula B or Formula C such as those disclosed in U.S. Pat. No. 3,303,139, the entire disclosure of which is incorporated herein by reference.
- Suitable acids of this type include methylenediphosphonic acid; ethylidenediphosphonic acid; isopropylidenediphosphonic acid; 1- hydroxy, ethylidenediphosphonic acid; hexamethylenediphosphonic acid; trimethylenediphosphonic acid; decamethylenediphosphonic acid; l-hydroxy, propylidenediphosphonic acid; 1,6-dihydroxy, 1,6- dimethyl, hexamethylenediphosphonic acid; 1,4- dihydroxy, 1,4-diethyl, tetramethylenediphosphonic acid; 1,3-dihydroxy, 1,3-dipropyl, trimethylenediphosphonic acid; 1,4-dibutyl, tetramethylenediphosphonic acid, dihydroxy, diethyl, ethylenediphosphonic acid;
- the water-soluble salts of these acids such as the alkali metal, alkaline earth metal, zinc, cobalt, chromium, lead, tin, nickel, ammonium, or amine and lower alkanol amine salts can be used.
- esters of these acids with an aliphatic alcohol having from 1 to 4 carbons, or mixtures of the above acids, salts or esters can be used. Use of mixtures of any of the general types of organo-phosphonic acid compounds described above is also contemplated within the scope of this invention.
- R4 OH OH where R is independently selected from the group con sisting of an alkyl group up to four carbon atoms and phosphonate groups, and R is selected from the group consisting of alkyl groups having up to four carbon atoms, when R is a phosphonate group and where n is 0 to 6, when R is an alkyl group; and watersoluble salts thereof.
- methanol phosphonic acid compounds thus disclosed include, for example, l-hydroxy ethylidene diphosphonic acid (i.e., ethanol, or methyl methanol, 1,1-diphosphonic acid); l-hydroxy, propylidene diphosphonic acid (i.e., ethyl methanol diphosphonic acid); l,6-dihydroxy-l,6-dimethyl, hexamethylene diphosphonic acid (i.e., tetramethylene bis( methyl methanol phosphonic acid)) and its sodium salt (Examples 44 and 100); 1,4-dihydroxy-l,4-diethyl, tetramethylene diphosphonic acid (i.e., dimethylene bis(ethylmethanol phosphonic acid)); l,3-dihydroxy-I,3-dipropyl trimethylene diphosphonic acid (i.e., methylene bis (propylmethanol phosphonic acid)) and its sodium salt (Example
- compositions of this invention also contain from 1 to 95 and preferably from 25 to 45 percent of a water-soluble zinc salt.
- a water-soluble zinc salt such as zinc nitrate (Zn(NO molecular weight 189) zinc chloride (ZnCl molecular weight 136.29) and zinc sulfate (ZnSO or ZnSO -H O, molecular weight 161.44 and 179.44, respectively) in the aforesaid concentrations will provide zinc ion (Zn" concentrations from as little as 0.345 weight percent (as 1 percent Zn(NO to as high as 45.5 weight percent (equivalent to percent ZnCl).
- the weight ratio of zinc (in the form of one of said water-soluble salts) to phosphonic acid compound may range from about 0.345280 to about 45.521 or, in other words, from about 1:232 to about 110.022.
- the weight ratio of zinc ion may range from about 8.64:80 (Zn equivalent in 25 weight percent of Zn(NO to about 21.5:1 (Zn equivalent in 45 weight percent of ZnClor in other words, from about 11927 to about 120.0465.
- a typical zinc to phosphonic acid compound weight ratio is 1:1.
- the zinc salts which can be employed in the composition of this invention include any water-soluble zinc salt such as zinc sulfate, zinc chloride, zinc nitrate, alkali metal-zinc phosphate glasses, crystalline alkali metalzinc polyphosphates, and the like.
- Aqueous systems can be treated with aqueous solutions containing from 1 to 70 percent and preferably from 1 to 10 percent of the compositions of this invention. These solutions can be made by premixing the ingredients of this composition and then adding the mixture to water, or by adding the individual ingredients of the composition of this invention separately to water. These aqueous feed solutions are stable and can be stored prior to use.
- the aqueous corrosion resistant solutions of this invention are solutions of at least 1 and preferably from 5 to 200 ppm. of the compositions of this invention.
- the ingredients can be added to the aqueous solution either in premixed solid or solution or individual solids or solutions to form this aqueous solution composition.
- compositions of this invention are non-toxic and prevent corrosion of metals in contact with aqueous liquids. These compositions can be substituted for chromate base corrosion inhibitors previously used where the toxicity of the chromate makes its use undesirable or where disposal of corrosion inhibiting solutions containing chromates raises serious water pollution problems requiring extensive pretreatment to remove the chromates prior to disposal of such solutions.
- the compositions of this invention in aqueous solutions prevent corrosion of metal parts such as heat exchangers, engine jackets, and pipes and particularly prevent metal loss, pitting, and tuberculation of iron base alloys, copper alloys, and aluminum alloys in contact with water.
- EXAMPLE 1 This example demonstrates the synergistic reduction in corrosion rates obtained with the compositions of this invention.
- the circulating water was fed to a closed circulating test system at a rate of 5 gallons per day, the ove rflow from the test system being discharged to waste.
- circulating water having a temperature of 130 F. and pH of 6.5-7.0 was fed at a rate of one gallon per minute to a coupon chamber containing test coupons for the corrosion test.
- Water from the coupon chamber was then passed through an arsenical admirality brass tube surrounded by a jacket through which a heating fluid having an initial temperature of 240 F. was countercurrently passed.
- the circulating water was then cooled to 130 F. and recirculated through the system. The total circulating time for each test was days.
- Example 4 corresponding to the composition of this invention provides a corrosion protection far greater than would be expected in view of the effects of the individual components thereof.
- a composition useful for inhibiting corrosion in aqueous systems consisting essentially of one part by weight zinc in the form of a watersoluble zinc salt and from 0.02 to about 300 parts by weight of a water-soluble organic phosphonate compound having the formula where R is independently selected from the group consisting of alkyl groups up to four carbon atoms, and phosphonate groups, and R is selected from the group consisting of alkyl groups having up to four carbon atoms, when R is a phosphonate group; and
- n is 0 to 6, when R is an alkyl group; and watersoluble salts and esters thereof.
- composition of claim 1 in which the watersoluble zinc salt is zinc sulfate.
- composition of claim 1 in which the phosphonate compound is ethanol 1,1-diphosphonicacid or water-soluble salt thereof.
- a method of inhibiting corrosion in aqueous systems comprising adding to said aqueous systems at least about one part per million of the composition of claim 1.
- a method of inhibiting corrosion in aqueous systems comprising adding to said aqueous system at least about one part per million of the composition of claim 2.
- a method of inhibiting corrosion in aqueous systems comprising adding to said aqueous system at least about one part per million of the composition of claim 3.
Abstract
Description
Claims (5)
- 2. The composition of claim 1 in which the water-soluble zinc salt is zinc sulfate.
- 3. The composition of claim 1 in which the phosphonate compound is ethanol 1,1-diphosphonic acid or water-soluble salt thereof.
- 4. A method of inhibiting corrosion in aqueous systems comprising adding to said aqueous systems at least about one part per million of the composition of claim 1.
- 5. A method of inhibiting corrosion in aqueous systems comprising adding to said aqueous system at least about one part per million of the composition of claim 2.
- 6. A method of inhibiting corrosion in aqueous systems comprising adding to said aqueous system at least about one part per million of the composition of claim 3.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00300938A US3803048A (en) | 1966-09-22 | 1972-10-26 | Organic phosphonic acid compound corrosion protection in aqueous systems |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US58115166A | 1966-09-22 | 1966-09-22 | |
US64560067A | 1967-06-13 | 1967-06-13 | |
US00300938A US3803048A (en) | 1966-09-22 | 1972-10-26 | Organic phosphonic acid compound corrosion protection in aqueous systems |
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US3803048A true US3803048A (en) | 1974-04-09 |
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US00300938A Expired - Lifetime US3803048A (en) | 1966-09-22 | 1972-10-26 | Organic phosphonic acid compound corrosion protection in aqueous systems |
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Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3888626A (en) * | 1971-08-19 | 1975-06-10 | Petrolite Corp | Use as corrosion inhibitors: phenanthridine phosphonic compounds |
US3979704A (en) * | 1975-05-23 | 1976-09-07 | Westinghouse Electric Corporation | Circuit breaker having members coated with phosphate-chromate protective layers |
US4018701A (en) * | 1975-07-31 | 1977-04-19 | Calgon Corporation | Phosphorous acid and zinc corrosion inhibiting compositions and methods for using same |
US4061589A (en) * | 1977-01-17 | 1977-12-06 | Chemed Corporation | Corrosion inhibitor for cooling water systems |
US4098749A (en) * | 1977-03-24 | 1978-07-04 | Dai Nippon Toryo Co., Ltd. | Anticorrosion primer coating composition |
US4134959A (en) * | 1976-05-10 | 1979-01-16 | Chemed Corporation | Azole-phosphate corrosion inhibiting composition and method |
US4209487A (en) * | 1975-06-02 | 1980-06-24 | Monsanto Company | Method for corrosion inhibition |
EP0084593A1 (en) * | 1982-01-25 | 1983-08-03 | Pennwalt Corporation | Phosphate conversion coatings for metals with reduced weights and crystal sizes |
US4479878A (en) * | 1982-10-28 | 1984-10-30 | Betz Laboratories, Inc. | High calcium tolerant deposit control method |
US4497713A (en) * | 1982-04-01 | 1985-02-05 | Betz Laboratories | Method of inhibiting corrosion and deposition in aqueous systems |
US4649025A (en) * | 1985-09-16 | 1987-03-10 | W. R. Grace & Co. | Anti-corrosion composition |
US4663053A (en) * | 1982-05-03 | 1987-05-05 | Betz Laboratories, Inc. | Method for inhibiting corrosion and deposition in aqueous systems |
US4810405A (en) * | 1987-10-21 | 1989-03-07 | Dearborn Chemical Company, Limited | Rust removal and composition thereof |
US4911887A (en) * | 1988-11-09 | 1990-03-27 | W. R. Grace & Co.-Conn. | Phosphonic acid compounds and the preparation and use thereof |
US4981648A (en) * | 1988-11-09 | 1991-01-01 | W. R. Grace & Co.-Conn. | Inhibiting corrosion in aqueous systems |
US5017306A (en) * | 1988-11-09 | 1991-05-21 | W. R. Grace & Co.-Conn. | Corrosion inhibitor |
US5266722A (en) * | 1988-11-09 | 1993-11-30 | W. R. Grace & Co.-Conn. | Polyether bis-phosphonic acid compounds |
US6299983B1 (en) | 1997-06-27 | 2001-10-09 | E. I. Du Pont De Nemours And Company | Derivatized metallic surfaces, composites of functionalized polymers with such metallic surfaces and processes for formation thereof |
-
1972
- 1972-10-26 US US00300938A patent/US3803048A/en not_active Expired - Lifetime
Cited By (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3888626A (en) * | 1971-08-19 | 1975-06-10 | Petrolite Corp | Use as corrosion inhibitors: phenanthridine phosphonic compounds |
US3979704A (en) * | 1975-05-23 | 1976-09-07 | Westinghouse Electric Corporation | Circuit breaker having members coated with phosphate-chromate protective layers |
US4209487A (en) * | 1975-06-02 | 1980-06-24 | Monsanto Company | Method for corrosion inhibition |
US4018701A (en) * | 1975-07-31 | 1977-04-19 | Calgon Corporation | Phosphorous acid and zinc corrosion inhibiting compositions and methods for using same |
US4134959A (en) * | 1976-05-10 | 1979-01-16 | Chemed Corporation | Azole-phosphate corrosion inhibiting composition and method |
US4061589A (en) * | 1977-01-17 | 1977-12-06 | Chemed Corporation | Corrosion inhibitor for cooling water systems |
US4098749A (en) * | 1977-03-24 | 1978-07-04 | Dai Nippon Toryo Co., Ltd. | Anticorrosion primer coating composition |
EP0084593A1 (en) * | 1982-01-25 | 1983-08-03 | Pennwalt Corporation | Phosphate conversion coatings for metals with reduced weights and crystal sizes |
US4427459A (en) | 1982-01-25 | 1984-01-24 | Pennwalt Corporation | Phosphate conversion coatings for metals with reduced coating weights and crystal sizes |
US4497713A (en) * | 1982-04-01 | 1985-02-05 | Betz Laboratories | Method of inhibiting corrosion and deposition in aqueous systems |
US4663053A (en) * | 1982-05-03 | 1987-05-05 | Betz Laboratories, Inc. | Method for inhibiting corrosion and deposition in aqueous systems |
US4479878A (en) * | 1982-10-28 | 1984-10-30 | Betz Laboratories, Inc. | High calcium tolerant deposit control method |
US4649025A (en) * | 1985-09-16 | 1987-03-10 | W. R. Grace & Co. | Anti-corrosion composition |
US4810405A (en) * | 1987-10-21 | 1989-03-07 | Dearborn Chemical Company, Limited | Rust removal and composition thereof |
US4911887A (en) * | 1988-11-09 | 1990-03-27 | W. R. Grace & Co.-Conn. | Phosphonic acid compounds and the preparation and use thereof |
US4981648A (en) * | 1988-11-09 | 1991-01-01 | W. R. Grace & Co.-Conn. | Inhibiting corrosion in aqueous systems |
US5017306A (en) * | 1988-11-09 | 1991-05-21 | W. R. Grace & Co.-Conn. | Corrosion inhibitor |
US5266722A (en) * | 1988-11-09 | 1993-11-30 | W. R. Grace & Co.-Conn. | Polyether bis-phosphonic acid compounds |
US5312953A (en) * | 1988-11-09 | 1994-05-17 | W. R. Grace & Co.-Conn. | Polyether bis-phosphonic acid compounds |
US6299983B1 (en) | 1997-06-27 | 2001-10-09 | E. I. Du Pont De Nemours And Company | Derivatized metallic surfaces, composites of functionalized polymers with such metallic surfaces and processes for formation thereof |
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Legal Events
Date | Code | Title | Description |
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AS | Assignment |
Owner name: DEARBORN CHEMICAL COMPANY 300 GENESEE STREET, LAKE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:CHEMED CORPORATION, A CORP. OF DE;REEL/FRAME:003963/0418 Effective date: 19820310 |
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STCF | Information on status: patent grant |
Free format text: PATENTED FILE - (OLD CASE ADDED FOR FILE TRACKING PURPOSES) |
|
AS | Assignment |
Owner name: W.R. GRACE & CO. Free format text: MERGER;ASSIGNOR:DEARBORN CHEMICAL COMPANY;REEL/FRAME:004528/0776 Effective date: 19851219 |
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AS | Assignment |
Owner name: W.R. GRACE & CO.-CONN. Free format text: MERGER;ASSIGNORS:W.R. GRACE & CO., A CORP. OF CONN. (MERGED INTO);GRACE MERGER CORP., A CORP. OF CONN. (CHANGED TO);REEL/FRAME:004937/0001 Effective date: 19880525 |