EP0162491B1 - Procédé pour inhiber la corrosion d'une masse métallique au contact d'un bain acide contenant des ions ferriques - Google Patents

Procédé pour inhiber la corrosion d'une masse métallique au contact d'un bain acide contenant des ions ferriques Download PDF

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Publication number
EP0162491B1
EP0162491B1 EP85200527A EP85200527A EP0162491B1 EP 0162491 B1 EP0162491 B1 EP 0162491B1 EP 85200527 A EP85200527 A EP 85200527A EP 85200527 A EP85200527 A EP 85200527A EP 0162491 B1 EP0162491 B1 EP 0162491B1
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EP
European Patent Office
Prior art keywords
bath
stack
process according
ferric ions
felts
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
Application number
EP85200527A
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German (de)
English (en)
French (fr)
Other versions
EP0162491A1 (fr
Inventor
Daniel Tytgat
Pierre Lefèvre
Dominique Balthasart
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.)
Solvay SA
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Solvay SA
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Filing date
Publication date
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Priority to AT85200527T priority Critical patent/ATE31083T1/de
Publication of EP0162491A1 publication Critical patent/EP0162491A1/fr
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Publication of EP0162491B1 publication Critical patent/EP0162491B1/fr
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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
    • C23F15/00—Other methods of preventing corrosion or incrustation
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions

Definitions

  • the present invention relates to a method for inhibiting the corrosion of metallic masses in contact with acid baths containing ferric ions, for example an industrial installation subjected to a descaling operation, or metallurgical products subjected to a pickling operation.
  • Corrosion inhibitors commonly used for this purpose are alkylpyridinium chlorides, hexamethylenetetramine and organic compounds comprising sulfonium groups.
  • corrosion inhibitors in the acid baths, these nonetheless cause rapid corrosion of the treated metallic masses. This corrosion would be due to the presence of oxidants in the bath mainly ferric ions.
  • reducing agents for example stannous chloride, in addition to corrosion inhibitors.
  • reducers in the bath is generally expensive, especially in the case of non-deaerated baths because there is then an appreciable loss in reducers, due to their untimely consumption by the oxygen of the bath, this consumption being all the more important. that the temperature is higher. It also results in an increase in the contamination of the bath by reducing agents, some of which, in particular stannous ions, are generally considered dangerous for the ecology, in particular when the residual baths are discharged into lakes or watercourses. .
  • the invention aims to remedy the aforementioned drawbacks by providing a method for inhibiting corrosion of metallic masses in contact with acid baths containing ferric ions, which is reliable, economical and harmless for the environment.
  • the invention therefore relates to a method for inhibiting corrosion of a metallic mass in contact with an acid bath containing ferric ions; according to the invention, at least part of the bath is circulated through a stack of non-graphitic carbon or graphite felts, alternating with solid bodies of iron or an iron alloy.
  • the method according to the invention applies to any acid bath containing ferric ions, capable of causing an electrochemical oxidation of the metal mass under the conditions of use of the bath.
  • the ferric ions present in the bath can come from very diverse sources such as, for example, from oxidized layers on the surface of the metallic mass, from corrosion of the bath handling circuit, from incrustation on the surface of the metallic mass, of impurities present in the acid bath; in the case of aqueous acid baths, ferric ions can sometimes be provided by the water used for the preparation of the bath.
  • a fraction of the bath is periodically removed and it is circulated through the stack for a predetermined time sufficient to reduce at least part of the ferric ions which it contains; the fraction is then returned to the bath.
  • a second treatment method which is preferred, the entire bath is circulated through the packing, at a rate adjusted so that at the exit of the stack, its ferric ion content has fallen below d 'a predetermined value.
  • the bath can be circulated through the stack periodically or continuously.
  • the treatment of the bath in the stack is generally governed, so that the residual quantity of ferric ions in the bath in contact with the metallic mass does not exceed 300 mg / 1, preferably 200 mg / 1. Residual contents not exceeding 150 mg / I are recommended, especially those between 1 and 100 mg / I.
  • a stack is used in which the felts are formed of fibers whose diameter does not exceed 25 microns, preferably 15 microns. It is preferred to use stacks of mild steel bodies and non-graphitic carbon felts, the fiber diameter of which is between 8 and 12 microns.
  • the solid bodies of the stack can have any profile allowing a large contact surface with the felts.
  • a stack is used in which the solid bodies of iron or of iron alloy are plates which alternate with carbon or graphite felts.
  • a stack is used in which the solid bodies are perforated plates and the bath is circulated through the stack, in a direction transverse to the plates and the felts.
  • the bath is circulated through the stack, in a direction transverse to the plates and the felts.
  • the method according to the invention also applies to acid baths containing a corrosion inhibitor.
  • a corrosion inhibitor may be, for example, alkylpyridinium chloride which is advantageously selected from those derived from alkanes having from 10 to 18 carbon atoms.
  • alkylpyridinium chloride which is advantageously selected from those derived from alkanes having from 10 to 18 carbon atoms.
  • cetyl-, myristil- or laurylpyridinium chloride in an amount regulated between 0.5 and 5000 mg per kg of the bath, preferably between 2 and 500 mg / kg.
  • corrosion inhibitors which can be used in the baths treated by the process according to the invention are hexamethylenetetramine and formalin.
  • the method according to the invention applies to any metallic mass treated in an acid bath containing ferric ions capable of attacking the metallic mass. It applies in particular to metallic masses comprising iron, chromium, zinc, cobalt, nickel or an alloy containing at least one of these metals. It finds a particularly interesting application in the case of metallic masses treated with aqueous baths of mineral acid containing ferric ions. It is particularly applicable to descaling, by means of such baths, of nickel or nickel alloy evaporators used to crystallize sodium chloride from caustic brines produced by electrolysis of sodium chloride brine in a cell. permeable diaphragm electrolysis.
  • the acid bath can for example be an aqueous solution of sulfuric acid or hydrochloric acid.
  • Aqueous solutions containing from 0.01 to 6 moles of hydrochloric acid per liter are generally suitable.
  • the installation shown diagrammatically in FIG. 1 comprises a pickling tank 1, containing a mass of ordinary steel or cast iron 2 to be pickled. This consists, for example, of a stack of coils of drawn wires or of strips.
  • the pickling is carried out by means of a bath 3 consisting of a normal hydrochloric acid solution.
  • the pickling tank is connected, by means of a pump 4 and pipes 5 and 6, to a treatment cell 7.
  • a treatment cell 7 This is formed (fig. 2) of a vertical tubular chamber 8 containing a stack of perforated horizontal steel discs 9, alternating with horizontal felt 10 made of non-graphitic carbon fibers.
  • the discs 9 are crossed by tubular vertical perforations 11.
  • the bath 3 is circulated from the tank 1 to the cell 7, via the pipes 5 and 6 and the pump 4.
  • the circulation of the bath 3 in the cell 7 can be carried out periodically or continuously.
  • the bath circulates in the perforations 11 in contact with the discs 9 and through the felts 10, and the ferric ions are reduced to ferrous ions.
  • an electrochemical measuring cell comprising a rotating platinum electrode and a fixed platinum counter electrode, immersed in the hydrochloric acid bath, and a calomel reference electrode, saturated with KCI ; by means of a potentiostatic circuit, the rotating electrode was maintained at a constant potential of - 150 mV relative to the reference electrode and the intensity of the electric current in the measuring cell was measured, which is substantially proportional to the concentration of ferric ions.
  • the abscissa scale indicates the time, in minutes, and the ordinate scale indicates the concentration of the bath in ferric ions, expressed in g / I.
  • the stack consisted of thirteen cast iron discs alternating with polyvinyl chloride rings.
  • the flow rate of the solution through the stack was 150 l / h.
  • the results of the test are reproduced on the curve (12) of the diagram in FIG. 3.
  • Example 5 a stack of perforated steel discs (of area equal to 20 cm 2) was used alternating with graphite felts.
  • the number of graphite felts was 6 in Example 3 and 12 in Example 4, respectively.
  • Example 5 two stacks of 13 discs (and 12 felts) were used, the two stacks being mounted in bypass on the hydrochloric acid solution circuit.
  • the flow rate of the solution was 200 l / h in each test.
  • Example 8 The conditions of Example 8 were repeated, using two identical stacks (13 steel discs and twelve carbon felts) arranged in parallel in the solution circuit. The results of the test are reproduced by the curve (20) of the diagram of FIG. 5. It is observed there that 8 minutes are sufficient to bring the content of ferric ions in the bath, from 10 g / 1 to 0.1 g / 1 .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Cosmetics (AREA)
EP85200527A 1984-04-16 1985-04-04 Procédé pour inhiber la corrosion d'une masse métallique au contact d'un bain acide contenant des ions ferriques Expired EP0162491B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85200527T ATE31083T1 (de) 1984-04-16 1985-04-04 Verfahren zur korrosionsinhibierung einer metallmasse,die in beruehrung steht mit einem saeurebad,das eisen iii-ionen enthaelt.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8406098 1984-04-16
FR8406098A FR2562914A1 (fr) 1984-04-16 1984-04-16 Procede pour inhiber la corrosion d'une masse metallique au contact d'un bain acide contenant un oxydant

Publications (2)

Publication Number Publication Date
EP0162491A1 EP0162491A1 (fr) 1985-11-27
EP0162491B1 true EP0162491B1 (fr) 1987-11-25

Family

ID=9303254

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85200527A Expired EP0162491B1 (fr) 1984-04-16 1985-04-04 Procédé pour inhiber la corrosion d'une masse métallique au contact d'un bain acide contenant des ions ferriques

Country Status (7)

Country Link
US (1) US4765958A (show.php)
EP (1) EP0162491B1 (show.php)
JP (1) JPS60234983A (show.php)
AT (1) ATE31083T1 (show.php)
DE (1) DE3561072D1 (show.php)
ES (1) ES542242A0 (show.php)
FR (1) FR2562914A1 (show.php)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6432197A (en) * 1987-07-29 1989-02-02 Hitachi Ltd Plant for retreatment of nuclear fuel
NL8900106A (nl) * 1989-01-18 1990-08-16 Avf Chemische Ind En Handelson Werkwijze voor het reinigen van metalen, bijvoorbeeld ijzeren of stalen, inwendige oppervlakken van industriele apparatuur.
US6329206B1 (en) * 1999-06-22 2001-12-11 Henkel Corporation Method of determining inhibitor concentrations in inhibited acidic pickling solutions
US9896738B2 (en) 2015-05-28 2018-02-20 Savannah River Nuclear Solutions, Llc Process for dissolving aluminum for recovering nuclear fuel

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL6406533A (show.php) * 1964-06-09 1965-12-10
JPS502372A (show.php) * 1973-05-15 1975-01-10
DE2457235A1 (de) * 1974-12-04 1976-06-10 Peter Vodicka Verwendung von metallen und/oder wasserloeslichen chemischen verbindungen zum schutz der in sauren inhibierten loesungen vom zunder gebeizten oder von eisen-iii-haltigen belaegen chemisch gereinigten metallischen gegenstaenden und/oder geschlossenen anlagen vor dem angriff der ferrikationen und anordnung zum erreichen dieses schutzes
JPS5215496A (en) * 1975-07-28 1977-02-05 Mitsubishi Electric Corp Method for production of ferrous nitrate

Also Published As

Publication number Publication date
ATE31083T1 (de) 1987-12-15
JPH0465908B2 (show.php) 1992-10-21
US4765958A (en) 1988-08-23
JPS60234983A (ja) 1985-11-21
FR2562914A1 (fr) 1985-10-18
EP0162491A1 (fr) 1985-11-27
ES8603596A1 (es) 1985-12-16
ES542242A0 (es) 1985-12-16
DE3561072D1 (en) 1988-01-07

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