US3257159A - Prevention of corrosion of wet metal articles - Google Patents

Prevention of corrosion of wet metal articles Download PDF

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Publication number
US3257159A
US3257159A US424263A US42426365A US3257159A US 3257159 A US3257159 A US 3257159A US 424263 A US424263 A US 424263A US 42426365 A US42426365 A US 42426365A US 3257159 A US3257159 A US 3257159A
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Prior art keywords
hydrazine
cyanide
liter
metal
heavy metal
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US424263A
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Zimmermann Max
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Bayer AG
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Bayer AG
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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
    • C23F11/18—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 inorganic inhibitors
    • C23F11/181—Nitrogen 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
    • C23F11/18—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 inorganic inhibitors
    • C23F11/187—Mixtures of inorganic inhibitors

Definitions

  • the present invention relates to the prevention of corrosion of wet metal articles, and more particularly to a process for the wet preservation and corrosion protection of metal articles which are in contact with an aqueous phase and to preparations for such purposes.
  • hydrazine as a corrosion protective agent, for example in steam boilers, hot water plants, etc. is already known.
  • the effect of this compound is attributed to the reactivity which has long been known to exist between hydrazine and the oxygen dissolved in water.
  • hydrazine has an effect on the formation of a protective layer on metal surfaces.
  • this effect is explained by the formation of a very thick, firmly adhering layer of Fe O A-t normal temperature, the rate of reaction of hydrazine with oxygen is very low.
  • the effect of hydrazine as a corrosion protective agent, especially on bare metal surfaces, leaves much to be desired, especially if chlorides or sulfates are dissolved in the water.
  • a further object of the present invention is to provide a'method for the wet preservation and corrosion protection of metal articles which are in contact with an aqueous phase normally corrosive thereto, especially after prolonged contact therewith, using a particular mixture of ingredients having a combined beneficial effect.
  • an aqueous phase such as an oxygen containing water and/or a salt containing water
  • FIG. 1 shows a graph illustrating the reaction between hydrazine and oxygen in an open system over an extended period of time in the presence or absence of complex heavy metal alkali cyanides
  • FIG. 2 shows a graph illustrating the reduction in oxygen content in a closed system by reason of the presence of hydrazine in the presence or absence of complex heavy metal alkali cyanides.
  • a process for the wet preservation and corrosion protection of metal articles in contact with an aqueous phase may be provided by means of hydrazine in the presence of activating substances, according to which hydrazine (preferably hydrazine hydrate) is added Patented June 21, 1966 in quantities of 0.1 to 3000 mg./liter of water and complex heavy metal cyanides are added in quantities of 0.1 to 10 mg./liter, preferably 0.1 to 5 rug/liter of water to the aqueous phase in contact with such metal articles.
  • hydrazine preferably hydrazine hydrate
  • Complex cyanides of monovalent copper, trivalent cobalt, divalent nickel, monovalent silver and divalent iron have proved to be especially effective.
  • the complex cyanides are used in the form of their alkali metal (e.g. sodium, potassium and lithium) compounds or their ammonium compounds.
  • the heavy metal cyanides must be present in a form which has no oxidizing effect on hydrazine. The complex-forming metals are therefore used in the lowest stage of oxidation in which they are stable under normal conditions. 7
  • FIGURE 2 shows the reduction of oxygen by hydrazine in the presence of cyanide complexes in a closed system at normal temperature (20 (3.).
  • water which was supersaturated with oxygen to provide an 0 concentration initially of 40 mg./ liter was kept in a closed measuring flask and in addition, mg. of hydrazine per liter were added in the form of a 24% solution of hydrazine hydrate and 10 mg./ liter of copper, iron and nickel, respectively, were added in the form of their complex alkali cyanides.
  • the reduction in oxygen was then measured by the same method as in the examples of FIGURE 1 by polarographic determinations over a period of 24 hours.
  • FIGURE 2 which covers a closed system, shows the same type of results as FIGURE 1, which covers an open system.
  • the reduction in oxygen in each instance is considerably greater than that in the blank sample due to the presence of the heavy metal cyanides.
  • curve 1 denotes the blank
  • curve 2 the example with the addition of Ni(II) in the form of Na [Ni(CN)
  • curve 4 the addition of Fe(lI) in the form of K [Fe (CN)
  • the influence of the activators together with hydrazine on an accelerated formation of a protective layer on the metal surfaces is also of importance since it was found that the heavy metal complexes of nickel and silver which, compared with the corresponding copper complexes, have a relatively very low effect on the reduction in oxygen, show approximately the same effect as such other heavy metal complexes (e.g., copper complexes) in corrosion protection tests.
  • the quantity of hydrazine calculated to give a concentration of 0.1 to 3000 mg./liter in water is added, preferably in the form of 24% hydrazine hydrate, to the feed or cooling water, etc., which is in contact with the metal to be protected.
  • a concentration of about 0.1 mg./liter water is sufiicient for degasified feed water, for example in boilers, whereas a concentration of about 300 rug/liter is preferred for water used in cooling circuits which generally contains a significant quantity of oxygen therein.
  • Higher hydrazine contents are not harmful in accordance with the present invention but are avoided normally because of economical considerations.
  • the complex heavy metal cyanides are added, preferably in the form of aqueous solutions of their alkali' metal or ammonium compounds.
  • a sufiicient protective effect is provided if the complexes are present in quantities of 0.01 to 10 mg./liter water calculated on the metal. It is preferred, however, to use a quantity of 0.1 to 5.0 mg/liter water.
  • the heavy metals of Groups 1b7b and 8 which form water-soluble alkali metal cyanide complexes and which metals are not reduced by hydrazine under the resulting conditions to the metal itself may be used in the form of their alkali cyanide complexes such as those of the heavy metals: copper, silver, zinc, cadmium, tungsten, chromium, manganese, iron cobalt and nickel.
  • the same may comprise an alkali component which may be defined as an alkali metal, such as sodium, potassium, lithium, etc., or ammonium.
  • alkali component which may be defined as an alkali metal, such as sodium, potassium, lithium, etc., or ammonium.
  • specific compounds usable herein as complex heavy metal cyanides therefore, are Na [Cu(CN) K [Cu(CN)
  • the copper cyanide complexes are used in systems containing water having a temperature below 60 C. At temperatures above 60 C. the nickel, cobalt and iron complexes are preferred, since they are more stable towards reduction by hydrazine.
  • the present process can therefore be used advantageously for the wet preservation and corrosion protection of steam producers, hot water plants, coolers using water as circulating medium and heat exchangers. It is especially advantageous that the preserving effect occurs at water temperatures at which only insuflicient protection of the metal surfaces was produced by the methods hitherto used, i.e., at temperatures of below C. or more precisely below the boiling point of the water up to the freezing point, however this temperature is no limitation of the new process for the hydrazine mixed with the aforesaid complex cyanides is applicable also to systems containing hot water or hot water and steam.
  • EXAMPLE 1 This test shows the effect of the cyanides on the degree of protection against corrosion of bare metal surfaces.
  • Pieces of boiler tubes or rings of iron quality St. 35.29 were annealed for 2 hours at 600 C. without tension and pickled until bare in 10% hydrochloric acid containing 0.1% of urotropin (hexamethylene tetramine).
  • the pretreated rings were suspended in an aqueous solution containing 200 mg. of N H per liter and 100 mg. of NaCl per liter.
  • the addition of sodium chloride served to increase the corrosive action of the water.
  • the samples were kept for 14 days in Erlen meyer flasks closed with rubber stoppers.
  • Sample 1 contains no activator additive, and Sample 2 contains 0.5 mg. of Na [Cu (CN) per liter. While Sample 1 undergoes pitting with severe corrosion, Sample 2 shows a black layer of Fe O without any pitting.
  • EXAMPLE 2 A heating circuit charged with ordinary salt-containing water having an N H concentration of 100 mg. per
  • Ni as activator additive in the form of the ('NH [Ni(CN) complex shows no sign of corrosion after being left to stand over the summer and can be put into operation again with the .water thus treated.
  • EXAMPLE 4 A closed cooling circuit containing softened or fully desalted water which has been treated with the addition corrosion protection of metal articles, such as those made of ferrous metals, in contact with an aqueous phase such as water containing oxygen and/ or inorganic salts such as chlorides, sulfates and nitrates of the alkali and alkaline earth metals, which comprises providing in such aqueous phase which is in contact with the particular metal article, both hydrazine in an amount substantially between about 0.13000 mg./liter and a complex heavy metal cyanide in an amount, calculated on the heavy metal, substantially between about 0.01-10 mg./liter.
  • the hydrazine is used in the form of hydrazine hydrate, as for example in the form of substantially about a 24% solution, and the complexheavy metal cyanide is present preferably in an amount,
  • the complex heavy metal cyanide is selected from the group consisting of the alkali metalmonovalent copper-cyanide, alkali metal-trivalent cohalt-cyanide, alkali metal-divalent nickel-cyanide, alkali metal-monovalent silver-cyanide, alkali metal-divalent iron-cyanide, ammonium-monovalent copper-cyanide, am-
  • the present invention represents an improvement in the method for the wet preservation and corrosion protection of predominantly iron-containing metals in contact with a solution containing at least one of oxygen and salt which normally cause corrosion, which improvement comprises maintaining in such solution when in contact with the particular rnetal article, a mixture of hydrazine and a complex heavy metal cyanide in ac cordance with the foregoing.
  • the present invention relates to a preparation for the wet preservation and corrosion protection of metal articles in contact with an aqueous phase, such preparation comprising a mixture in an aqueous solution of hydrazine and a complex heavy metal cyanide in amounts per liter as stated above.
  • Such preparation contemplates complex heavy metal cyanides such as those selected from the foregoing enumerated group and in particular preparations may be used which contain in aqueous solution a mixture of hydrazine in an amount substantially between about 0.1-3000 mg./liter with substantially between about 0.01- mg./liter, calculated on the particular heavy metal, of Na Cu(CN)
  • said complex heavy metal cyanide is selected from the group consisting of alkali metal-monovalent copper-cyanide, alkali metaltrivalent cobalt-cyanide, alkali metal-divalent nickel-cyanide, alkali metal-monovalent silver-cyanide, alkali'metaldivalent iron-cyanide, ammonium-monovalent copper-cyanide, ammonium-trivalent cobalt-cyanide, ammonium-divalent nickel-cyanide, ammonium-monovalent silver-cyanide, ammonium-divalent iron-cyanide, and mixtures thereof.
  • hydrazine is used in the form of substantially about a 24% hydrazine hydrate solution and said cyanide is present in an amount, calculated on the heavy metal, substantially between about 0.l-5 mg./liter of the aqueous phase.
  • aqueous phase which comprises a mixture in aqueous solution of hydrazine in an amount substantially between about 0.1- 3000 mg./liter and a complex heavy metal cyanide in an amount, calculated on the heavy metal, substantially between about 0.0l10 mg./liter.
  • hydrazine is present in the form of substantially about a 24% hydrazine hydrate solution and said cyanide is present in an amount, calculated on the heavy metal, sub stantially between about 0.1-5 mg./kg. of the 24% hydrazine hydrate solution present.
  • said complex heavy metal cyanide is selected from the group consisting of alkali metal-monovalent copper-cyanide, alkali metal-trivalent cobalt-cyanide, alkali metal-divalent nickel-cyanide, alkali metal-monovalent silver-cyanide, alkali metal-divalent iron-cyanide, ammonium-monovalent copper-cyanide, ammonium-trivalent cobalt-cyanide, ammonium-divalent nickel-cyanide, ammonium-monovalent silver-cyanide, ammonium-divalent iron-cyanide, and mixtures thereof.
  • aqueous phase which comprises a mixture in aqueous solution 7 of hydrazine in an amount substantially between about 0.1-3000 mg./liter and Na Cu(CN) in an amount, calculated on the copper, substantially between about 0.01- 10 mg./liter.
  • an aqueous phase which comprises a mixture in aqueous solution of hydrazine in an amount substantially between about 0.1- 3000 mg./liter and (NH Ni(CN) in an amount, calculated on the nickel, substantially between about 0.01- 10 mg./liter.
  • an aqueous phase which comprises a mixture in aqueous solution of hydrazine in an amount substantially between about 0.1- 3000 mg./liter and Na Ni(CN) in an amount, calculated on the nickel, substantially between about 0.01-10 mg./ liter.
  • aqueous phase which comprises a mixture in aqueous solution of hydrazine in an amount substantially between about 0.1- 3000 mg./liter and Na Fe(CN) in an amount, calculated 5 on the iron, substantially between about 0.0ll0 mg./ liter.

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
US424263A 1964-01-23 1965-01-08 Prevention of corrosion of wet metal articles Expired - Lifetime US3257159A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3919000A (en) * 1973-06-15 1975-11-11 Pennwalt Corp Preanneal rinse process for inhibiting rust on steel strip
FR2540854A1 (fr) * 1983-04-22 1984-08-17 Leuna Werke Veb Procede pour l'elimination de l'oxygene dissous dans l'eau

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1260740A (en) * 1917-08-02 1918-03-26 William H Allen Treatment of iron and steel to prevent corrosion.
US2901437A (en) * 1955-05-03 1959-08-25 Wright Chem Corp Corrosion inhibiting composition
US3151087A (en) * 1957-12-09 1964-09-29 Nalco Chemical Co Corrosion inhibiting compositions and method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1260740A (en) * 1917-08-02 1918-03-26 William H Allen Treatment of iron and steel to prevent corrosion.
US2901437A (en) * 1955-05-03 1959-08-25 Wright Chem Corp Corrosion inhibiting composition
US3151087A (en) * 1957-12-09 1964-09-29 Nalco Chemical Co Corrosion inhibiting compositions and method

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3919000A (en) * 1973-06-15 1975-11-11 Pennwalt Corp Preanneal rinse process for inhibiting rust on steel strip
FR2540854A1 (fr) * 1983-04-22 1984-08-17 Leuna Werke Veb Procede pour l'elimination de l'oxygene dissous dans l'eau

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AT255228B (de) 1967-06-26
BE658678A (en(2012)) 1965-07-22
NL6500664A (en(2012)) 1965-07-26
LU47724A1 (en(2012)) 1965-03-05

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