EP1558787B1 - Verfahren zur inhibierung der interkristalline korrosion von metalloberflächen - Google Patents

Verfahren zur inhibierung der interkristalline korrosion von metalloberflächen Download PDF

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Publication number
EP1558787B1
EP1558787B1 EP03749550A EP03749550A EP1558787B1 EP 1558787 B1 EP1558787 B1 EP 1558787B1 EP 03749550 A EP03749550 A EP 03749550A EP 03749550 A EP03749550 A EP 03749550A EP 1558787 B1 EP1558787 B1 EP 1558787B1
Authority
EP
European Patent Office
Prior art keywords
recited
corrosion
spray water
metal surfaces
reaction product
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
EP03749550A
Other languages
English (en)
French (fr)
Other versions
EP1558787A1 (de
Inventor
Stuart D. Klatskin
Steven Weeden
Dino Colarossi
Chris Austin
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.)
Veolia WTS USA Inc
Original Assignee
GE Betz Inc
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
Application filed by GE Betz Inc filed Critical GE Betz Inc
Publication of EP1558787A1 publication Critical patent/EP1558787A1/de
Application granted granted Critical
Publication of EP1558787B1 publication Critical patent/EP1558787B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/12—Accessories for subsequent treating or working cast stock in situ
    • B22D11/124—Accessories for subsequent treating or working cast stock in situ for cooling
    • B22D11/1245—Accessories for subsequent treating or working cast stock in situ for cooling using specific cooling agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/12—Accessories for subsequent treating or working cast stock in situ
    • B22D11/124—Accessories for subsequent treating or working cast stock in situ for cooling
    • 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

Definitions

  • the present invention is directed to the use of the reaction product of alkynediols and polyalkylene polyamine compounds to inhibit intergranular corrosion of metal surfaces in industrial water and process systems, which surfaces are in contact with spray water or condensation.
  • the microstructure of metals and alloys is made up of grains, separated by grain boundaries. Intergranular corrosion may be defined as localized attack along the grain boundaries, or immediately adjacent to grain boundaries. Such precipitation can produce zones of reduced corrosion resistance in the immediate vicinity.
  • Chromium-rich grain boundary precipitates lead to a local depletion of Cr adjacent to these precipitates, leaving these areas vulnerable to corrosive attack.
  • Exfoliation corrosion is a particular form of intergranular corrosion. Exfoliation or delainination presents itself as a loss of metal in layers that appear to follow grain boundaries along the surface.
  • the exfoliation in the casters for instance, occurs on the non-wetted structures of the lower segments where direct spray water contact does not occur.
  • the steel is exposed to a hot, humid environment in which the surfaces are wetted only by spray water mist or condensation. The corrosion propagates rapidly along the steel surfaces, resulting in the loss of structural integrity of the secondary supporting structure.
  • the mechanism for exfoliation corrosion is related to the presence of chlorides in the spray water.
  • mist steam
  • the heat and humidity evaporates the water from the steel surface, leaving behind a concentrated chloride ion. This process continues, concentrating more and more chloride ions to the point where exfoliation occurs.
  • Coupon analysis reveals that the corrosion mechanism occurs as follows: The chloride ion that is deposited on the metal surface migrates through the brittle layer of corrosion product/deposit that is generated. Under the deposit, a transient iron chloride salt is generated. The salt is hygroscopic (moisture absorbing) and undergoes hydrolysis, creating acid chloride conditions. Additional iron oxide corrosion products are left behind as the acidic corrosion front advances deeper into the metal surface.
  • the present invention is directed toward methods for inhibiting the intergranular corrosion of metal surfaces in industrial processing systems, e.g., steam and cooling water systems, which surfaces are in contact with spray water or condensation, which comprises adding to the spray water a sufficient corrosion inhibiting amount of the reaction product of an alkynediol and a polyalkylene polyamine.
  • the alkynediols and alkenediols taught to be effective in producing the reaction product are those containing four to twelve carbon atoms.
  • the alkynediols contain four carbon atoms.
  • An exemplary alkynediol is butynediol.
  • the polyalkylene polyamine compounds taught to be effective in producing the reaction product are those containing two to ten amine groups, and preferably, three to seven amine groups. These amine groups may be substituted or unsubstituted, and each is separated by an alkylene group having from one to six carbon atoms, with two to four being preferred.
  • Exemplary polyamines include ethylene diamine, diethylene triamine, pentaethylene hexamine, pentapropylene hexamine, triheptylene diamine, and the like.
  • the weight ratio of the reactants are such as to attain full reaction between the respective ingredients with weight ratios of amine to diol of 4:1 to 1:1, with 3:1 being preferred.
  • An ionizable compound of copper, such as copper acetate, is employed in this reaction in catalytic amounts.
  • the reaction product of the present invention may be added to the spray water in an amount which is sufficient to inhibit corrosion of the metal surfaces.
  • the reaction product may be added to a supply line in an amount ranging from 0.5 parts to about 500 parts per million parts of water present in the supply line. Preferably, about 1 to 100 parts per million parts water are added, with about 5 to 10 parts per million parts water particularly preferred.
  • the reaction product of the present invention is added to the supply line in either a solvent or in neat form.
  • the reaction product is added in an aqueous solvent, of which water is an example.
  • the reaction product can be added to the spray water along with other suitable ingredients, such as antifoams, corrosion inhibitors, and the like.
  • the spray water is typically at a temperature of from about 43,3 - 82,2°C (110 - 180 °F) in the systems to be treated.
  • a corrosion coupon was dipped in Product A and placed next to an untreated coupon in both the treated and untreated strands.
  • the dipped coupon showed very little corrosion, while the untreated coupon was exfoliated.
  • the treated strand there was a significant improvement in corrosion control versus the undipped coupon.
  • Coupons tested included: mild steel, stainless steel, copper and coated mild steel.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (13)

  1. Verfahren zur Inhibierung der Intergranularkorrosion von Metalloberflächen in industriellen Verarbeitungssystemen, wobei die Oberflächen in Kontakt mit Spritzwasser sind, welches Verfahren umfasst, dass man dem Spritzwasser eine zur Inhibierung der Korrosion ausreichende Menge des Umsetzungsproduktes eines Alkindiols und eines Polyalkylenpolyamins hinzufügt.
  2. Verfahren nach Anspruch 1 , wobei die Intergranularkorrosion schichtförmige Korrosionen ist.
  3. Verfahren nach Anspruch 1, wobei die Metalloberflächen kontinuierliche Gießflächen umfassen.
  4. Verfahren nach Anspruch 2, wobei die schichtförmige Korrosion auf Metalloberflächen geschieht, die durch Spritzwassemebel oder Kondensation benetzt sind.
  5. Verfahren nach Anspruch 1, wobei das Alkindiol eine Alkingrupppe enthält, die 4 bis 12 Kohlenstoffatome hat.
  6. Verfahren nach Anspruch 1, wobei das Alkindiol Butindiol ist.
  7. Verfahren nach Anspruch 1, wobei das Polyalkylenpolyamin 2 bis 10 Amingruppen enthält, die jeweils durch eine Alkylengruppe von einander getrennt sind, die 1-6 Kohlenstoffatome hat.
  8. Verfahren nach Anspruch 1, wobei das Polyalkylenpolyamin Pentaethylenhexamin ist.
  9. Verfahren nach Anspruch 1, wobei das Reaktionsprodukt dem Spritzwasser in einer Menge im Bereich von 0,5 Teilen bis etwa 500 Teilen pro Million Wasserteilen zugefügt wird.
  10. Verfahren nach Anspruch 1, wobei das Spritzwasser eine Temperatur von etwa 43,3°C (110°F) bis etwa 82,2°C (180°F) hat.
  11. Verfahren nach Anspruch 1, wobei das Reaktionsprodukt dem Spritzwasser in einem wässrigen Lösungsmittel zugefügt wird.
  12. Verfahren nach Anspruch 1, wobei die Metalloberflächen Eisen enthaltende Metalloberflächen sind.
  13. Verfahren nach Anspruch 1, wobei die industriellen Verarbeitungsverfahren Dampf- und Kühlwassersysteme umfassen.
EP03749550A 2002-10-30 2003-09-10 Verfahren zur inhibierung der interkristalline korrosion von metalloberflächen Expired - Lifetime EP1558787B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US283457 2002-10-30
US10/283,457 US20040086419A1 (en) 2002-10-30 2002-10-30 Methods for inhibiting intergranular corrosion of metal surfaces
PCT/US2003/028266 WO2004042115A1 (en) 2002-10-30 2003-09-10 Methods for inhibiting intergranular corrosion of metal surfaces

Publications (2)

Publication Number Publication Date
EP1558787A1 EP1558787A1 (de) 2005-08-03
EP1558787B1 true EP1558787B1 (de) 2007-02-28

Family

ID=32174660

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03749550A Expired - Lifetime EP1558787B1 (de) 2002-10-30 2003-09-10 Verfahren zur inhibierung der interkristalline korrosion von metalloberflächen

Country Status (17)

Country Link
US (1) US20040086419A1 (de)
EP (1) EP1558787B1 (de)
JP (1) JP4424671B2 (de)
KR (1) KR101058965B1 (de)
CN (1) CN100425735C (de)
AT (1) ATE355402T1 (de)
AU (1) AU2003267075B2 (de)
BR (1) BR0315190B1 (de)
CA (1) CA2504421A1 (de)
DE (1) DE60312202T2 (de)
ES (1) ES2282654T3 (de)
NZ (1) NZ540134A (de)
PL (1) PL376482A1 (de)
RU (1) RU2320778C2 (de)
UA (1) UA80451C2 (de)
WO (1) WO2004042115A1 (de)
ZA (1) ZA200503934B (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MD307Z (ro) * 2010-04-27 2011-07-31 Институт Прикладной Физики Академии Наук Молдовы Inhibitor de coroziune a oţelului în apă
RU2754319C1 (ru) * 2020-12-14 2021-09-01 Федеральное государственное бюджетное образовательное учреждение высшего образования "Башкирский государственный университет" Способ получения ингибиторов коррозии на основе тетрапропиленпентаминов для нефтепромыслового оборудования и трубопроводов
RU2754326C1 (ru) * 2020-12-14 2021-09-01 Федеральное государственное бюджетное образовательное учреждение высшего образования "Башкирский государственный университет" Способ получения бис-имидазолинов и их производных на основе пентаэтиленгексаминов для коррозионной защиты нефтепромыслового оборудования и трубопроводов

Family Cites Families (13)

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Publication number Priority date Publication date Assignee Title
US2923599A (en) * 1958-03-26 1960-02-02 Universal Oil Prod Co Water-soluble corrosion inhibitors
US3113113A (en) * 1958-11-07 1963-12-03 Armour & Co Corrosion inhibitor compositions
GB894386A (en) * 1959-04-20 1962-04-18 Continental Oil Co Polyamine-diol reaction products and corrosion inhibiting compositions containing same
US3152187A (en) * 1960-04-13 1964-10-06 Continental Oil Co Condensation product of unsaturated diols and polyalkylene polyamines and method of preparation thereof
US3211667A (en) * 1960-04-13 1965-10-12 Continental Oil Co Corrosion inhibition
US3320318A (en) 1963-08-19 1967-05-16 Continental Oil Co Thiobenzene-diol-polyamine corrosion inhibiting composition
FR2477923A1 (fr) * 1980-03-11 1981-09-18 Compiegne Universite Technolog Procede de refroidissement par pulverisation d'eau en coulee continue ou dans des domaines techniques voisins
DE3317126C2 (de) * 1983-05-06 1986-07-24 Mannesmann AG, 4000 Düsseldorf Verfahren zur Vermeidung von Säurekorrosion an Stranggießanlagen
SU1681736A3 (ru) * 1990-03-30 1991-09-30 Oleg A Povarov Cпocoб meжoпepaциohhoй зaщиtы ot koppoзии пapoboдяhыx tpaktob tуpбoуctahobkи и уctpoйctbo для eгo ocущectbлehия
SU1728305A1 (ru) * 1990-05-07 1992-04-23 Центральная научно-исследовательская лаборатория Производственного объединения "Укрнефть" Композици дл ингибировани коррозии металлов в водных средах
US5173213A (en) * 1991-11-08 1992-12-22 Baker Hughes Incorporated Corrosion and anti-foulant composition and method of use
US5311925A (en) * 1993-11-12 1994-05-17 Nalco Chemical Company Magnesium hydroxide to prevent corrosion caused by water spray in continuous casting
CA2123936C (en) * 1994-04-06 2005-12-27 Bruno E. Morin Methods of inhibiting water corrosion in crude oil pipelines

Also Published As

Publication number Publication date
JP4424671B2 (ja) 2010-03-03
BR0315190A (pt) 2005-08-23
AU2003267075B2 (en) 2009-06-25
KR20050083872A (ko) 2005-08-26
EP1558787A1 (de) 2005-08-03
US20040086419A1 (en) 2004-05-06
CN100425735C (zh) 2008-10-15
KR101058965B1 (ko) 2011-08-23
AU2003267075A1 (en) 2004-06-07
ATE355402T1 (de) 2006-03-15
ES2282654T3 (es) 2007-10-16
UA80451C2 (en) 2007-09-25
PL376482A1 (en) 2005-12-27
JP2006504870A (ja) 2006-02-09
DE60312202D1 (de) 2007-04-12
BR0315190B1 (pt) 2013-02-05
WO2004042115A1 (en) 2004-05-21
NZ540134A (en) 2006-10-27
DE60312202T2 (de) 2007-10-31
RU2320778C2 (ru) 2008-03-27
ZA200503934B (en) 2006-08-30
CN1714173A (zh) 2005-12-28
CA2504421A1 (en) 2004-05-21
RU2005116268A (ru) 2006-02-10

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