EP0592118A1 - Verfahren zur Korrosions- und biologischen Substanzkontrolle in Kühlwassersystemen aus Kupfer und Kupferlegierungen - Google Patents

Verfahren zur Korrosions- und biologischen Substanzkontrolle in Kühlwassersystemen aus Kupfer und Kupferlegierungen Download PDF

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Publication number
EP0592118A1
EP0592118A1 EP93307345A EP93307345A EP0592118A1 EP 0592118 A1 EP0592118 A1 EP 0592118A1 EP 93307345 A EP93307345 A EP 93307345A EP 93307345 A EP93307345 A EP 93307345A EP 0592118 A1 EP0592118 A1 EP 0592118A1
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EP
European Patent Office
Prior art keywords
triazole
copper
cooling water
ppm
oxidizing biocide
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Granted
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EP93307345A
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English (en)
French (fr)
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EP0592118B1 (de
Inventor
Frank F Y Lu
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ChampionX LLC
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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

  • This invention relates generally to corrosion control and, more particularly, to a method of controlling corrosion of copper and copper alloys in cooling water systems, in the presence of oxidizing biocides.
  • Corrosion occurs when metals are oxidized to their respective soluble ions or insoluble salts. Metal loss due to solubilization can cause the structural integrity of the system to deteriorate over time. This can cause leakage between the water system and process streams. Also, the formation of insoluble salts in the corrosion process can produce a build-up of deposits which impede heat transfer and fluid flow.
  • Triazoles such as tolyltriazole and benzotriazole are commonly used in cooling water systems as corrosion inhibitors for yellow metals, namely copper and copper alloys.
  • triazoles are continuously fed into a recirculating cooling water system for inhibiting corrosion of copper and copper alloys. The purpose of this continuous feed is to maintain a low level of triazole first to form and then to maintain a protective triazole layer.
  • the continuous feed method is too expensive to apply to once-through and high blowdown rate cooling water systems since large amounts of water are discharged from these systems in a short period of time. It would be both economically and environmentally unsound to continuously discharge such high volumes of triazole-loaded cooling water.
  • U.S. Patent No. 4,744,950 discloses the use of an alkyl benzotriazole to form a protective film on copper and copper alloys in cooling water systems by intermittently feeding the alkyl benzotriazole into once-through and high blowdown rate cooling water systems. While it is claimed in this patent that a corrosion inhibitive film is formed which will stand up to overfeeds of oxidizing biocides, it is also acknowledged that corrosion inhibitive films formed using benzotriazole and tolytriazole will be destroyed in the presence of the oxidizing biocides.
  • Oxidizing biocides are commonly added to cooling water systems. They are an inexpensive, yet effective means by which to control the formation of biological matter such as algae and bacteria. Chlorinating and brominating agents, which are the most widely used biocides in the cooling water treatment industry, are commonly fed intermittently. Unfortunately, as already noted, oxidizing biocides disrupt tolyltriazole and benzotriazole corrosion inhibitive films. More particularly, chlorine (OClO ⁇ HClO) and bromine (OBrO ⁇ , HOBr) penetrate and attack prefilmed triazole surfaces, thereby destroying the effectiveness of such cuprous metal corrosion inhibitors. Tolyltriazole and benzotriazole protective films are especially susceptible to attack by oxidizing biocides.
  • This invention entails a method of controlling corrosion and biological matter, especially in once-through and high blowdown rate cooling water systems,by establishing a protective triazole film on copper and copper alloy surfaces and then intermittently introducing a combination of a low level of triazole and an oxidizing biocide. Additionally, the corrosion rates and copper concentrations in the system discharge should be continuously monitored to determine if the formation of subsequent protective triazole films on the copper or copper alloy is required, and sufficient triazole should then be added, as required.
  • the present invention is thus economically appealing, environmentally acceptable, and effective in controlling not only corrosion, but biological matter, such as algae and bacteria, as well.
  • a protective triazole film is established on a copper or copper alloy surface.
  • Tolyltriazole, benzotriazole, or C1 to C12 alkyl substituted benzotriazoles may be used as the cuprous metal corrosion inhibitor.
  • Tolyltriazole is preferred.
  • the triazole should be present in the system water at a level ranging from about 0.5 to 50 ppm by weight for a time period of at least about 2 hours, and preferably in the range of about 3 to 5 ppm for about 4 to 48 hours.
  • a low level of triazole is introduced into the cooling water system along with the oxidizing biocide.
  • Tolyltriazole, benzotriazole, C1 to C12 alkyl substituted benzotriazoles, or other commercially available triazoles may be used as the cuprous metal corrosion inhibitor. Tolyltriazole is preferred.
  • the corrosion rates and copper concentrations in the discharge are then continuously monitored with a suitable device such as a corrater, until it is determined that the formation of another subsequent protective triazole film on the copper or copper alloy is required. When this occurs, sufficient triazole is added to raise the level to at least about 0.5 to 50 ppm for at least about 2
  • Copper electrodes were prefilmed by immersing them in a 5 ppm tolyltriazole solution for about 20 hours. The prefilmed electrodes were then subjected to 12 cycles of intermittent NaOBr treatment. Each cycle included a 2 hour immersion in a 1 ppm free residual chlorine (FRC) NaOBr solution followed by a 22 hour immersion in tap water, which was aerated at room temperature.
  • FRC free residual chlorine
  • Corrosion rates were then obtained by taking linear polarization resistance measurements in the tap water.
  • the polarization resistance data were converted to mpy (mils per year of metal loss) using equation (1), where Rp represents polarization resistance.
  • the corrosion rate at each of the 12 cycles of intermittent NaOBr treatment is plotted in FIGURE 1. The corrosion rates were unacceptable, as will be evident to those skilled in the art.
  • Example 2 The same procedure as described in Example 1 was followed, except that each cycle also included the simultaneous addition of 0.5 ppm tolyltriazole with the 1 ppm (FRC) NaOBr solution.
  • FIGURE 2 illustrates that the corrosion rates decreased significantly when the tolyltriazole was added simultaneously with the NaOBr.
  • a comparison of FIGURES 1 and 2 indicates that superior corrosion control is achieved when a low level of tolyltriazole is simultaneously added during intermittent NaOBr treatment.
  • Admiralty electrodes were prefilmed by immersing them in a 5 ppm tolytriazole or 5 ppm butylbenzotriazole solution for about 20 hours.
  • the blank was a freshly polished admiralty electrode with 600 grit SiC which was etched with 10% H2SO4.
  • the prefilmed and blank electrodes were then subjected to 6 cycles of intermittent NaOBr treatment. Each cycle included a 2 hour immersion in a 10 ppm (FRC) NaOBr solution followed by a 22 hour immersion in tap water, which was aerated at room temperature.
  • FRC 10 ppm
  • Example 3 The same procedure as described in Example 3 was followed, except that each cycle also included the simultaneous addition of either 0.2 ppm tolyltriazole, 0.5 ppm tolytriazole, 1.0 ppm tolytriazole, or 2.0 ppm tolytriazole with the 10 ppm (FRC) NaOBr solution.
  • FIGURE 4 shows that the corrosion rates decreased significantly when the tolyltriazole was added simultaneously with the NaOBr. A comparison of FIGURES 3 and 4 indicates that superior corrosion control is achieved when a low level of tolyltriazole is introduced along with the intermittent NaOBr treatment.

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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)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
EP19930307345 1992-10-08 1993-09-17 Verfahren zur Korrosions- und biologischen Substanzkontrolle in Kühlwassersystemen aus Kupfer und Kupferlegierungen Expired - Lifetime EP0592118B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US95855392A 1992-10-08 1992-10-08
US958553 1992-10-08

Publications (2)

Publication Number Publication Date
EP0592118A1 true EP0592118A1 (de) 1994-04-13
EP0592118B1 EP0592118B1 (de) 1996-07-31

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EP19930307345 Expired - Lifetime EP0592118B1 (de) 1992-10-08 1993-09-17 Verfahren zur Korrosions- und biologischen Substanzkontrolle in Kühlwassersystemen aus Kupfer und Kupferlegierungen

Country Status (4)

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EP (1) EP0592118B1 (de)
JP (1) JPH06212459A (de)
BR (1) BR9304164A (de)
DE (1) DE69303874T2 (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996029449A1 (en) * 1995-03-21 1996-09-26 Betzdearborn Inc. Methods of inhibiting corrosion using n-halo-azoles
AU706221B2 (en) * 1995-03-21 1999-06-10 Betzdearborn Inc. Methods of inhibiting corrosion using N-haloazoles
EP1288336A1 (de) * 2001-08-02 2003-03-05 Rohm And Haas Company Verfahren zu Inhibierung von Korrosion in wässrigen Systemen mit Halogen behandelten aromatischen Azolen
KR100407673B1 (ko) * 2000-12-29 2003-12-01 박혜서 지열을 이용한 냉난방 시스템 및 대형 열교환 말뚝 시공방법
US6840251B2 (en) 2002-04-30 2005-01-11 Nalco Company Methods of simultaneously cleaning and disinfecting industrial water systems
US7252096B2 (en) 2003-04-08 2007-08-07 Nalco Company Methods of simultaneously cleaning and disinfecting industrial water systems

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4959062B2 (ja) * 2001-02-28 2012-06-20 伯東株式会社 水系処理法
JP3832399B2 (ja) * 2001-08-28 2006-10-11 栗田工業株式会社 殺菌殺藻剤組成物及び水系の殺菌殺藻方法
JP5824841B2 (ja) * 2011-03-30 2015-12-02 栗田工業株式会社 銅系部材の腐食抑制方法
JP2012215410A (ja) * 2011-03-31 2012-11-08 Kurita Water Ind Ltd 銅系部材の耐食性試験方法
WO2019173123A1 (en) 2018-03-08 2019-09-12 General Electric Company Methods and compositions to reduce azoles and aox corrosion inhibitors

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB933979A (en) * 1961-04-27 1963-08-14 Ici Ltd Improvements in or relating to inhibiting corrosion of copper and copper-base alloys
EP0462809A1 (de) * 1990-06-20 1991-12-27 Calgon Corporation Verfahren zur Korrosionsinhibierung von Kupfer und Kupferlegierung mit Alkylbenzotriazol enthaltenden Zusammensetzungen
EP0478247A2 (de) * 1990-09-24 1992-04-01 Calgon Corporation Alkoxybenzotriazole Zusammensetzungen und Verwendung deren als Kupfer und Kupferlegierung Korrosionsinhibitoren
EP0479572A2 (de) * 1990-10-03 1992-04-08 Betz Europe, Inc. Korrosionsinhibierung für Kupfer oder Kupferenthaltende Metalle

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB933979A (en) * 1961-04-27 1963-08-14 Ici Ltd Improvements in or relating to inhibiting corrosion of copper and copper-base alloys
EP0462809A1 (de) * 1990-06-20 1991-12-27 Calgon Corporation Verfahren zur Korrosionsinhibierung von Kupfer und Kupferlegierung mit Alkylbenzotriazol enthaltenden Zusammensetzungen
EP0478247A2 (de) * 1990-09-24 1992-04-01 Calgon Corporation Alkoxybenzotriazole Zusammensetzungen und Verwendung deren als Kupfer und Kupferlegierung Korrosionsinhibitoren
EP0479572A2 (de) * 1990-10-03 1992-04-08 Betz Europe, Inc. Korrosionsinhibierung für Kupfer oder Kupferenthaltende Metalle

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996029449A1 (en) * 1995-03-21 1996-09-26 Betzdearborn Inc. Methods of inhibiting corrosion using n-halo-azoles
AU692089B2 (en) * 1995-03-21 1998-05-28 Betzdearborn Inc. Methods of inhibiting corrosion using N-halo-azoles
AU706221B2 (en) * 1995-03-21 1999-06-10 Betzdearborn Inc. Methods of inhibiting corrosion using N-haloazoles
KR100264419B1 (ko) * 1995-03-21 2000-08-16 리씨 알렉산더 디. 금속 표면의 부식 억제 방법
KR100407673B1 (ko) * 2000-12-29 2003-12-01 박혜서 지열을 이용한 냉난방 시스템 및 대형 열교환 말뚝 시공방법
EP1288336A1 (de) * 2001-08-02 2003-03-05 Rohm And Haas Company Verfahren zu Inhibierung von Korrosion in wässrigen Systemen mit Halogen behandelten aromatischen Azolen
US6840251B2 (en) 2002-04-30 2005-01-11 Nalco Company Methods of simultaneously cleaning and disinfecting industrial water systems
US8668779B2 (en) 2002-04-30 2014-03-11 Nalco Company Method of simultaneously cleaning and disinfecting industrial water systems
US7252096B2 (en) 2003-04-08 2007-08-07 Nalco Company Methods of simultaneously cleaning and disinfecting industrial water systems

Also Published As

Publication number Publication date
EP0592118B1 (de) 1996-07-31
DE69303874D1 (de) 1996-09-05
JPH06212459A (ja) 1994-08-02
BR9304164A (pt) 1994-04-12
DE69303874T2 (de) 1997-01-30

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