EP0215655B1 - Procédé d'inhibition de la corrosion de chaudières et compositions à cet effet - Google Patents

Procédé d'inhibition de la corrosion de chaudières et compositions à cet effet Download PDF

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Publication number
EP0215655B1
EP0215655B1 EP86307064A EP86307064A EP0215655B1 EP 0215655 B1 EP0215655 B1 EP 0215655B1 EP 86307064 A EP86307064 A EP 86307064A EP 86307064 A EP86307064 A EP 86307064A EP 0215655 B1 EP0215655 B1 EP 0215655B1
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EP
European Patent Office
Prior art keywords
oxygen
corrosion
trihydroxybenzene
compositions
boiler feedwater
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
EP86307064A
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German (de)
English (en)
Other versions
EP0215655A1 (fr
Inventor
John D. Zupanovich
Dennis J. Sepelak
Lois J. Neil
Rabindra K. Sinha
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.)
Ecc Specialty Chemicals Inc english China Clays
Calgon Corp
Original Assignee
Calgon Corp
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Publication date
Application filed by Calgon Corp filed Critical Calgon Corp
Priority to AT86307064T priority Critical patent/ATE49424T1/de
Publication of EP0215655A1 publication Critical patent/EP0215655A1/fr
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Publication of EP0215655B1 publication Critical patent/EP0215655B1/fr
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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
    • C23F11/08—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
    • C23F11/12—Oxygen-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
    • 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
    • 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
    • C23F11/144—Aminocarboxylic acids

Definitions

  • This invention relates to the inhibition of corrosion in boiler feedwater systems and boilers due to the presence of dissolved oxygen. It is also concerned with compositions for such use.
  • the first product of corrosion may be ferric oxide, which is only loosely adherent and blocks off areas to oxygen access. These areas become anionic and iron oxide couples are set up. The iron under the oxide deposit then dissolves, and pitting develops, which thus aggravates corrosion.
  • the severity of attack by oxygen will depend on the concentration of dissolved oxygen in the water, and the pH and temperature of the water. As the water temperature increases, corrosion in feed lines, heaters, boilers, steam and return lines made of iorn and steel increases.
  • a major approach to reducing oxygen in boiler feedwater is mechanical deaeration. Efficient mechanical deaeration can reduce dissolved oxygen to as low as 5-10 ppb (parts per thousand million) in industrial plants and 2-3 ppb in utility operations. However, even with this trace amount of oxygen, some corrosion may occur in boilers. Removal of the last traces of oxygen from boiler feedwater is generally accomplished by the addition of chemicals that react with oxygen and that are hereinafter referred to as oxygen scavangers.
  • oxygen scavengers e.g. sodium sulphite, hyrazine, diethylhydroxylamine, carbohydrazide and hydroquinone, as disclosed in numerous U.S. Patent Specifications.
  • US-A-3 551 349 discloses the use of quinones, particularly hydroquinone, as catalysts for the hydrazine-oxygen reaction;
  • US-A-4 096 090 discloses the use of hydrazine compounds, a catalytic organometallic complex, and preferably a quinone compound for deoxygenating feedwater;
  • US-A-3 808 138 discloses the use of cobalt maleic acid hydrazide with hydrazine for oxygen removal;
  • US-A-3 962 113 discloses the use of organic-substituted hydrazines such as monoalkyl hydrazines, dialkyl hydrazines and trialkyl hydrazines as oxygen scavengers.
  • hydrazine and related compounds include toxicity and suspected carcinogenicity.
  • Hydrazine is toxic if inhaled and is also an irritant to the eyes and skin.
  • Carbohydrazide which is a derivative of hydrazine, decomposes to form hydrazine and carbon dioxide at temperatures above 360°F (180°C).
  • US-A-4 269 717 discloses the use of carbohydrazide as an oxygen scavenger and metal passivator.
  • US-A-4 278 635 and US-A-4 282 111 disclose the use of hydroquinone, as well as other dihydroxy, diamino and amino hydroxy benzenes, as oxygen scavengers; US-A-4 279 767 and US-A-4 487 708 disclose the use of hydroquinone and "mu-amines", which are defined as amines compatible with hydroquinone, e.g. methoxypropylamine; US-A-4 363 734 discloses the use of catalysed 1,3-dihydroxyacetone as an oxygen scavenger; US-A-4 419 327 discloses the use of amine or ammonia neutralized erythorbates as oxygen scavengers.
  • DEHA diethylhydroxylamine
  • US-A-4 192 844 discloses the use of methoxypropylamine and hydrazine as a corrosion inhibiting composition.
  • European Patent Specification EP-A-0 054 345 discloses the use of amino-phenol compounds or acid addition salts thereof as oxygen scavangers.
  • UK Patent Specification GB-A-2 138796 discloses the use of trivalent phenols, preferably pyrogallol, to improve the activity of hydrazine/trivalent-cobalt compositions.
  • the present invention provides a method for controlling corrosion in boilers and boiler feedwater systems comprising adding to boiler feedwater containing dissolved oxygen an additive comprising at least one trihydroxybenzene compound and hydroquinone in a weight ratio in the range 1:99 to 99:1.
  • the present invention also provides a corrosion-inhibiting composition comprising at least one trihydroxybenzene compound and hydroquinone in a weight ratio in the range 1:99 to 99:1.
  • the additive can be used in conjunction with hydrazine, but this is not preferred because of the toxicity of hydrazine.
  • the preferred dosage in order to inhibit corrosion is from 0.1 to 1,000 parts per million in the feedwater being treated, particularly from 1 to 100 parts per million.
  • the preferred mol ratio of the compound to dissolved O2 ranges from 0.01:1.0 to 100.1, particularly 0.1:1 to 20:1.
  • trihydroxybenzene compound can be used, viz. (and in order of preference) 1,2,3-trihydroxybenzene (pyrogallol), 1,2,4-trihydroxybenzene (hydroxyhydroquinone), or 1,3,5-trihydroxybenzene (phloroglucinol).
  • the trihydroxybenzene compounds can if desired be used in combination with each other or with other known corrosion inhibitors, e.g. filming amines and neutralizing amines.
  • compositions of the present invention can be used in the compositions of the present invention if desired.
  • Such compounds include catalysts such as cobalt, scale/deposit inhibitors such as chelants, dispersants, sequestrants, polyelectrolytes and organic or inorganic phosphates.
  • compositions may be fed to the boiler feedwater by any known means. Thus, they may be pumped into boiler feedwater tanks or lines, or added by some other suitable means. Though for convenience it is recommended that the trihydroxybenzene and hydroquinone be added as a composition, they may be added separately.
  • Examples 1-11 show the oxygen scavenging capability of pyrogallol. Pyrogallol, at the concentration indicated in Table I below, was added to a simulated boiler feedwater at a pH of 9.0 and at the temperature shown. Percent oxygen removal vlaues after 2, 4, 6, 8 and 10 minutes are shown in Table I.
  • Examples 12-14 show the oxygen scavenging capability of 1,2,4-trihydroxybenzene (phloroglucinol), which was added to simulated boiler feedwater at pH 9 and at the temperatures and dosages shown. Percent oxygen removal values after 2, 4, 6, 8 and 10 minutes are shown in Table II, below.
  • oxygen scavengers as boiler water corrosion inhibitors
  • results can be misleading. This is true because, in operating systems, oxygen is an intermediary in the corrosion reaction and the first product of corrosion is ferric oxide. Oxygen alone would not necessarily be detrimental were it not for this corrosion reaction.
  • the primary function of an oxygen scavenger may therefore be to reduce ferric ions to their original state. Under such conditions, it is the iron itself that is the primary "oxygen scavenger"; the dosing agent functions primarily as a reducing agent for ferric ions.

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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)

Claims (6)

1. Procédé d'inhibition de la corrosion dans les chaudières et les systèmes d'alimentation en eau des chaudières comprenant d'ajouter à l'eau d'alimentation de chaudière contenant de l'oxygène dissout un additif comprenant au moins un composé trihydroxybenzène et l'hydroquinone dans un rapport pondéral compris dans l'intervalle de 1:99 à 99:1.
2. Procédé selon la revendication 1, dans lequel la quantité d'additif est comprise entre 0,1 ppm et 1 000 ppm par rapport à l'eau.
3. Procédé selon la revendication 2, dans lequel ladite quantité est comprise entre 1 et 100 ppm.
4. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel le composé trihydroxybenzène est le pyrogallol ou le 1,2,4-triohydroxybenzène.
5. Composition inhibant la corrosion comprenant au moins un composé trihydroxybenzène et l'hydroquinone dans un rapport pondéral compris dans l'intervalle de 2:99 à 99:1.
6. Composition selon la revendication 5, dans laquelle le composé trihydroxybenzène est le pyrogallol ou le 1,2,4-trihydroxybenzène.
EP86307064A 1985-09-17 1986-09-12 Procédé d'inhibition de la corrosion de chaudières et compositions à cet effet Expired - Lifetime EP0215655B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86307064T ATE49424T1 (de) 1985-09-17 1986-09-12 Verfahren zur korrosionsinhibierung in dampfkesseln und zusammensetzungen hierfuer.

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
US77693585A 1985-09-17 1985-09-17
US776935 1985-09-17
US79500985A 1985-11-04 1985-11-04
US795009 1985-11-04
US80134985A 1985-11-25 1985-11-25
US801349 1985-11-25

Publications (2)

Publication Number Publication Date
EP0215655A1 EP0215655A1 (fr) 1987-03-25
EP0215655B1 true EP0215655B1 (fr) 1990-01-10

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP86307064A Expired - Lifetime EP0215655B1 (fr) 1985-09-17 1986-09-12 Procédé d'inhibition de la corrosion de chaudières et compositions à cet effet

Country Status (5)

Country Link
EP (1) EP0215655B1 (fr)
JP (1) JP2617453B2 (fr)
AU (1) AU592367B2 (fr)
CA (1) CA1294420C (fr)
DE (1) DE3668190D1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2500835C1 (ru) * 2012-03-30 2013-12-10 Общество с ограниченной ответственностью "Научно-производственная фирма "ТРАВЕРС" (ООО "НПФ ТРАВЕРС") Ингибитор углекислотной коррозии для паро-конденсатных установок аминат пк-3
RU2516176C2 (ru) * 2012-03-30 2014-05-20 Общество с ограниченной ответственностью "Научно-производственная фирма "ТРАВЕРС" (ООО "НПФ ТРАВЕРС") Ингибитор углекислотной коррозии для паровых котлов среднего и высокого давления аминат пк-2
RU2557036C1 (ru) * 2014-04-11 2015-07-20 Фонд поддержки научной, научно-технической и инновационной деятельности "Энергия без границ" Комплексный реагент для обработки пароводяного тракта энергоблоков тэс

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01225785A (ja) * 1988-03-07 1989-09-08 Kurita Water Ind Ltd 洗浄水用鋼板変色防止剤
NZ229120A (en) * 1988-05-23 1991-09-25 Calgon Corp Inhibiting corrosion in caustic evaporators by using hydroquinone and pyrogallol
US5064469A (en) * 1989-10-03 1991-11-12 Akzo N.V. Preparation of oxidation resistant metal powder
JP2689059B2 (ja) * 1992-11-16 1997-12-10 小糸工業株式会社 身体障害者用座席
KR100315496B1 (ko) * 1997-08-13 2002-01-15 조민호 부식방지조성물을이용한보일러응축시스템의부식억제방법
KR100315497B1 (ko) * 1997-08-13 2002-01-17 조민호 보일러응축시스템의초기응축지역의부식억제방법
RU2447198C1 (ru) * 2010-09-27 2012-04-10 Государственное учреждение "Научно-исследовательский технологический институт гербицидов и регуляторов роста растений с опытно-экспериментальным производством Академии наук Республики Башкортостан" Способ ингибирования коррозии металлов
RU2543591C2 (ru) * 2013-07-19 2015-03-10 Открытое акционерное общество "Всероссийский дважды ордена Трудового Красного Знамени теплотехнический научно-исследовательский институт" Способ организации водно-химического режима на основе комплексного аминосодержащего реагента для пароводяного тракта энергоблока с парогазовыми установками
RU2702534C1 (ru) * 2017-11-16 2019-10-08 Публичное акционерное общество "Федеральная гидрогенерирующая компания - РусГидро" Система защиты от коррозии контура геотермальной электростанции с дополнительным смешиванием
CN111018028B (zh) * 2019-12-06 2022-01-28 南通联膦化工有限公司 一种环保型锅炉除氧剂
CN111233178A (zh) * 2020-02-27 2020-06-05 威海翔泽新材料科技有限公司 一种低压锅炉无磷复合清缸剂及制备方法

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU537619B2 (en) * 1980-04-28 1984-07-05 Betz International, Inc. Dioxo-aromatic compounds as oxygen scavengers in an aqueous medium
JPS57135086A (en) * 1981-02-13 1982-08-20 Nalco Chemical Co Method of removing dissolved oxygen from boiler water
US4419327A (en) * 1981-12-22 1983-12-06 Nalco Chemical Company Method of scavenging dissolved oxygen in steam generating equipment using ammonia or amine neutralized erythorbic acid
FR2522522A1 (fr) * 1982-01-27 1983-09-09 Leuna Werke Veb Procede pour ameliorer l'activite initiale de l'hydrazine activee
JPS58133382A (ja) * 1982-02-03 1983-08-09 Katayama Chem Works Co Ltd 塩化カルシウムブライン用防食剤
AU2804584A (en) * 1983-05-16 1984-11-22 Amchem Products Inc. Amine inhibitor to protect ferrous based cans

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Kirk-Othmer: Encyclopedia of Chemical Technology, 3rd. ed., vol. 18 (1982), p.681; vol. 24(1984, p.379 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2500835C1 (ru) * 2012-03-30 2013-12-10 Общество с ограниченной ответственностью "Научно-производственная фирма "ТРАВЕРС" (ООО "НПФ ТРАВЕРС") Ингибитор углекислотной коррозии для паро-конденсатных установок аминат пк-3
RU2516176C2 (ru) * 2012-03-30 2014-05-20 Общество с ограниченной ответственностью "Научно-производственная фирма "ТРАВЕРС" (ООО "НПФ ТРАВЕРС") Ингибитор углекислотной коррозии для паровых котлов среднего и высокого давления аминат пк-2
RU2557036C1 (ru) * 2014-04-11 2015-07-20 Фонд поддержки научной, научно-технической и инновационной деятельности "Энергия без границ" Комплексный реагент для обработки пароводяного тракта энергоблоков тэс

Also Published As

Publication number Publication date
JPS62116788A (ja) 1987-05-28
DE3668190D1 (de) 1990-02-15
EP0215655A1 (fr) 1987-03-25
JP2617453B2 (ja) 1997-06-04
AU6273486A (en) 1987-03-19
AU592367B2 (en) 1990-01-11
CA1294420C (fr) 1992-01-21

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