EP0600411A1 - Mikrobiologisch stabiler Buntmetall-Korrosionsinhibitor - Google Patents

Mikrobiologisch stabiler Buntmetall-Korrosionsinhibitor Download PDF

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Publication number
EP0600411A1
EP0600411A1 EP93119207A EP93119207A EP0600411A1 EP 0600411 A1 EP0600411 A1 EP 0600411A1 EP 93119207 A EP93119207 A EP 93119207A EP 93119207 A EP93119207 A EP 93119207A EP 0600411 A1 EP0600411 A1 EP 0600411A1
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EP
European Patent Office
Prior art keywords
weight
methylbenzotriazole
water
mbt
tolyltriazole
Prior art date
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Application number
EP93119207A
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English (en)
French (fr)
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EP0600411B1 (de
Inventor
Narashima M. Rao
Frank Y. Lu
Donald A. Johnson
Nhuan P. Nghiem
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.)
ChampionX LLC
Original Assignee
Nalco Chemical Co
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Publication date
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Application filed by Nalco Chemical Co filed Critical Nalco Chemical Co
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    • 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
    • C23F11/10—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 using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom

Definitions

  • the present invention is directed to a microbiologically stable corrosion inhibitor and a method of preventing yellow metal corrosion in aqueous systems.
  • the composition and method provide superior corrosion performance. More particularly, the invention provides a composition including 4-methylbenzotriazole (4-MBT) which is used as a yellow metal corrosion inhibitor in aqueous systems.
  • Tolyltriazole has two isomers, 4-methylbenzotriazole (4-MBT) and 5-methylbenzotriazole (5-MBT).
  • Tolyltriazole as the mixture of the two isomers, has traditionally been one of the most effective corrosion inhibitors for copper and its alloys in a wide variety of cooling water environments.
  • a commercially available preparation of the mixed tolyltriazole isomers is COBRATEC@ TT-100, available from PMC Specialties, Cincinnati, Ohio.
  • Mixed tolyltriazole isomer preparations used as corrosion inhibitors include at least 60% by weight of the 5-MBT isomer.
  • the tolyltriazole isomers are added to cooling water to inhibit corrosion.
  • the tolyltriazole isomers prevent corrosion by adsorbing to metal surfaces to produce a protective surface film which inhibits corrosion. It is believed that the surface film is a monolayer film.
  • the present invention advantageously provides a tolyltriazole composition which is not biodegradable and, therefore, will provide a corrosion inhibitor which is easier to dose, more economical and not wasted in systems which have microbiological contamination.
  • the novel composition and method of the present invention significantly and unexpectedly provide excellent corrosion inhibition while being microbiologically stable.
  • One aspect of the invention provides a method of preventing the corrosion of the yellow metal surfaces of a cooling system in contact with water.
  • the method comprises the step of adding to the water a tolyltriazole composition including at least 45 % by weight 4-methylbenzotriazole.
  • the 4-methylbenzotriazole is added to the water in a final concentration of from about 0,01 to about 100 parts per million.
  • the 4-methylbenzotriazole is added to the water either intermittently or continuously.
  • Other known non-tolyltriazole corrosion inhibitors may also be added to the water.
  • the invention provides a microbiologically stable corrosion inhibitor preferably for use of preventing the corrosion of cooling system surfaces in contact with water, in particular water containing microorganisms, and especially for use of preventing the corrosion of cooling system yellow metal surfaces in contact with water, in particular water containing microorganisms, which corrosion inhibitor comprises a tolyltriazole composition containing at least 45 % by weight of 4-methylbenzotriazole and less than 55 % by weight of 5-methylbenzotriazole, optionally in admixture with a non-tolyltriazole corrosion inhibitor.
  • the tolyltriazole composition includes at least 60 % by weight, preferably at least 80 % by weight, and most preferably at least 95 % by weight of 4-methylbenzotriazole, and less than 40 % by weight, preferably less than 20 % by weight, and most preferably less than 5 % by weight of 5-methylbenzotriazole.
  • the present invention provides a composition and a method of preventing the corrosion of cooling system yellow metal surfaces in contact with water.
  • cooling water systems such as cooling water towers, once-through cooling systems, cooling lake or pond systems, and spray ponds, are treated by the method and compositions of the invention. These cooling water systems are described in detail in the Nalco Water Handbook, 2nd ed., Ch. 34 (1988).
  • yellow metal is intended to include copper, bronze, and copper alloys.
  • the tolyltriazole composition of the invention includes at least 45% by weight of the 4-methylbenzotriazole (4-MBT) isomer of tolyltriazole.
  • 4-MBT 4-methylbenzotriazole
  • the present inventor has discovered that the 4-MBT isomer of tolyltriazole is biologically stable whereas the 5-methylbenzotriazole (4-MBT) isomer is not.
  • the 4-MBT is stable in cooling water including naturally occurring or added micro-organisms.
  • the tolyltriazole compositions of the invention include at least 60%, and more preferably, 80% by weight of the 4-MBT isomer. Most preferably, the tolyltriazole composition of the invention includes from about 90 to about 99% by weight of the 4-MBT isomer.
  • a tolyltriazole composition consisting essentially of the 4-MBT isomer is added to an industrial or commercial cooling system in an electric utility to prevent yellow metal corrosion.
  • the 4-MBT isomer is preferably added in a dosage of from 0.01 to about 100 parts per million (ppm). More preferably, the 4-MBT is added to the cooling water in a final concentration of from 0.1 to about 20 ppm.
  • the dosage of 4-MBT in the cooling water will depend on how corrosive the cooling water is, and on whether the yellow metal surfaces of the cooling water tower have been previously treated with corrosion inhibitors.
  • 4-MBT is added to the cooling water continuously at a controlled rate to maintain a concentration of from 0.01 - 100 ppm.
  • 4-MBT is biostable
  • 4-MBT is preferably added intermittently to achieve a concentration of 4-MBT in the water from 0.05 to about 20 ppm.
  • the cooling water may also contain non-tolyltriazole corrosion inhibitors, such as biocides, phosphates, benzotriazole, napthatriazole, molybdates, and polymer treatment programs. These other non-tolyltriazole corrosion inhibitors may be added with the 4-MBT or separately.
  • 5-MBT is biodegraded; however, 4-MBT is not effected.
  • 4-MBT adsorbs to yellow metal surfaces more effectively.
  • treatment with 4-MBT provides a better protective film over yellow metal surfaces; and therefore, provides a superior protective barrier against the corrosive cooling water.
  • 4-MBT is not biodegraded, the task of maintaining a constant protective concentration of 4-MBT in the cooling water is significantly simplified. Also, chemical is not wasted through biodegradation. Thus, the treatment of the invention is more economical to the operator.
  • the Examples below further show that unadsorbed 4-MBT is not biodegraded by microbes in a cooling tower or other cooling system. Therefore, the 4-MBT which is not biodegraded remains in the cooling water and continues to prevent corrosion.
  • the present invention prevents the loss of chemical seen using the mixed isomer preparations currently being used while providing superior protection against corrosion. Furthermore, the use of the present invention provides a constant concentration of corrosion inhibition in the water. Thus, cooling system operators are better able to control corrosion.
  • a field sample of discharge from a utility treated with a mixed tolyltriazole preparation was analyzed for 4- and 5-MBT using HPLC and found to contain only 4-MBT.
  • This sample was spiked with 2 ppm of a mixed isomer tolyltriazole (TT) preparation (1.16 ppm 5-MBT and 0.84 ppm 4-MBT). It was found that the 5-MBT levels had not changed in about ten hours. When measured at the end of 40 hours, 5-MBT had completely disappeared ( Figure 1).
  • 4-MBT levels on the other hand, remained constant throughout the experiment. This type of extremely selective degradation (5-MBT vs. 4-MBT) following an initial acclimation period, is very typical of microbiological processes. Addition of sulfuric acid (up to 15%), in order to lyse any bacteria, did not result in recovery of 5-MBT ruling out processes such as adsorption by cell walls.
  • a field sample from a utility was analyzed for TT by HPLC and found to contain only 4-MBT.
  • the sample was split into eight fractions. One fraction was left as is and spiked with 2 ppm TT. The other seven fractions were subjected to one of the following processes and then spiked with TT:
  • the eighth sample was spiked with 2 ppm TT and chilled in a refrigerator at 4 ° C. It was found that in the field sample with no treatment, 5-MBT disappeared in approximately 2 days. In samples 2 through 8, 5-MBT was stable for up to one month (analysis was not performed after this time). Since all the treatments listed in sample nos. 2 through 8 either have bactericidal effect or inhibit bacterial metabolism, preservation of 5-MBT in these samples seems to point to a microbiological mode of degradation When sample no. 8 (chilled sample) was kept at room temperature, the 5-MBT disappeared in about two days.
  • This example provides evidence of microbiological mechanism of degradation of 5-MBT.
  • the field water sample from Example 2 was split into four portions. The first portion was contained in a brown glass bottle and completely covered in aluminum foil. The second portion was contained in a transparent volumetric flask. The third portion was contained in a plastic bottle, and the fourth container was contained in a plastic bottle and covered with aluminum foil. All of the samples were spiked with 2 ppm of TT from Example 2. After two days, the samples were assayed for TT using HPLC. It was found that the 5-MBT isomer had disappeared in all of them However, 4-MBT concentrations did not change. This example illustrates that disappearance of the 5-MBT isomer is not due to a container effect (e.g. adsorption on plastic, etc.) or a photochemical phenomenon.
  • a container effect e.g. adsorption on plastic, etc.
  • a Pilot Cooling Tower water sample known to degrade 5-MBT was split into three parts. To the first portion, 5-MBT was repeatedly spiked (each time waiting for the previous spike to disappear). A cumulative concentration of 1050 ppm was spiked to this portion. Whenever 5-MBT was spiked to the first portion, the same concentration of 4-MBT was spiked to the second portion and distilled water was spiked to the third portion. Samples were withdrawn at various intervals and assayed for total aerobic counts and for 4- or 5-MBT using HPLC. The results showed that 5-MBT concentrations in the first portion decreased to zero following each spike of 5-MBT. However, 4-MBT concentrations in the second portion steadily increased, consistent with amount of 4-MBT spiked to the sample.
  • Figure 2 depicts total aerobic bacterial counts as a function of cumulative dosage of 4-MBT, 5-MBT and distilled water. It can be clearly seen that addition of 5-MBT to the first flask and its subsequent degradation results in a significant increase in total cell counts. No such increase was found for the 4-MBT isomer and the control sample.
  • the three solutions were then transferred to respirometry bottles and the oxygen consumption by the bacteria in the bottles was measured as a function of time. It was found that the 5-MBT spiked samples showed a significantly higher oxygen consumption (55 ppm per 50 ppm of 5-MBT) than 4-MBT and the distilled water spiked samples.
  • the 5-MBT spiked sample was repeatedly spiked with 100, 150, 200 and 250 ppm of 5-MBT, each time waiting for the oxygen consumption from the previous spike to level off. The results are shown in Figure 3.

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  • 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)
EP19930119207 1992-11-30 1993-11-29 Mikrobiologisch stabiler Buntmetall-Korrosionsinhibitor Revoked EP0600411B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US98300392A 1992-11-30 1992-11-30
US983003 1992-11-30

Publications (2)

Publication Number Publication Date
EP0600411A1 true EP0600411A1 (de) 1994-06-08
EP0600411B1 EP0600411B1 (de) 1997-01-29

Family

ID=25529735

Family Applications (1)

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EP19930119207 Revoked EP0600411B1 (de) 1992-11-30 1993-11-29 Mikrobiologisch stabiler Buntmetall-Korrosionsinhibitor

Country Status (5)

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EP (1) EP0600411B1 (de)
JP (1) JPH06212460A (de)
BR (1) BR9304871A (de)
DE (1) DE69307846T2 (de)
ES (1) ES2101201T3 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0698947A2 (de) 1994-08-25 1996-02-28 The Whitaker Corporation Elektrisches Kabelbaum mit elektrischem Verbinder mit elektrischem Bauteil darin und dessen Herstellungsverfahren
EP0716164A1 (de) * 1994-12-05 1996-06-12 Mitsui Mining & Smelting Co., Ltd. Kupferfolie behandelt mit einer organischen Korrosionsschutzmittel
EP0773298A1 (de) * 1995-11-09 1997-05-14 Nalco Chemical Company Überwachung der mikrobiologischen Aktivität in einem Flüssigkeitssystem

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63180562A (ja) * 1987-01-22 1988-07-25 Aisin Seiki Co Ltd 電動式パワ−ステアリングの誤動作防止装置

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH561290A5 (de) * 1970-11-13 1975-04-30 Ciba Geigy Ag
GB1398988A (en) * 1971-06-14 1975-06-25 Sherwin Williams Co Corrosion inhibitors
US4657785A (en) * 1985-12-11 1987-04-14 Nalco Chemical Company Use of benzo and tolyltriazole as copper corrosion inhibitors for boiler condensate systems

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH561290A5 (de) * 1970-11-13 1975-04-30 Ciba Geigy Ag
GB1398988A (en) * 1971-06-14 1975-06-25 Sherwin Williams Co Corrosion inhibitors
US4657785A (en) * 1985-12-11 1987-04-14 Nalco Chemical Company Use of benzo and tolyltriazole as copper corrosion inhibitors for boiler condensate systems

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Derwent World Patents Index; *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0698947A2 (de) 1994-08-25 1996-02-28 The Whitaker Corporation Elektrisches Kabelbaum mit elektrischem Verbinder mit elektrischem Bauteil darin und dessen Herstellungsverfahren
EP0716164A1 (de) * 1994-12-05 1996-06-12 Mitsui Mining & Smelting Co., Ltd. Kupferfolie behandelt mit einer organischen Korrosionsschutzmittel
US6071629A (en) * 1994-12-05 2000-06-06 Mitsui Mining & Smelting Co., Ltd. Organic rust-proof treated copper foil
EP0773298A1 (de) * 1995-11-09 1997-05-14 Nalco Chemical Company Überwachung der mikrobiologischen Aktivität in einem Flüssigkeitssystem

Also Published As

Publication number Publication date
DE69307846D1 (de) 1997-03-13
DE69307846T2 (de) 1997-08-28
BR9304871A (pt) 1994-06-21
ES2101201T3 (es) 1997-07-01
EP0600411B1 (de) 1997-01-29
JPH06212460A (ja) 1994-08-02

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