EP0157708B1 - Degreasing process for cold-rolled metal strip - Google Patents

Degreasing process for cold-rolled metal strip Download PDF

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Publication number
EP0157708B1
EP0157708B1 EP85400669A EP85400669A EP0157708B1 EP 0157708 B1 EP0157708 B1 EP 0157708B1 EP 85400669 A EP85400669 A EP 85400669A EP 85400669 A EP85400669 A EP 85400669A EP 0157708 B1 EP0157708 B1 EP 0157708B1
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EP
European Patent Office
Prior art keywords
degreasing
atmosphere
hydrogen
injected
steam
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Expired - Lifetime
Application number
EP85400669A
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German (de)
French (fr)
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EP0157708A3 (en
EP0157708A2 (en
Inventor
Robert Wang
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Fives Stein SA
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Stein Heurtey SA
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Priority claimed from FR8405366A external-priority patent/FR2562563B1/en
Priority claimed from FR8414950A external-priority patent/FR2571064B2/en
Application filed by Stein Heurtey SA filed Critical Stein Heurtey SA
Priority to AT85400669T priority Critical patent/ATE57396T1/en
Publication of EP0157708A2 publication Critical patent/EP0157708A2/en
Publication of EP0157708A3 publication Critical patent/EP0157708A3/en
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Publication of EP0157708B1 publication Critical patent/EP0157708B1/en
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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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B45/00—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B45/02—Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for lubricating, cooling, or cleaning
    • B21B45/0269—Cleaning
    • B21B45/0275—Cleaning devices
    • B21B45/0278—Cleaning devices removing liquids
    • B21B45/0284—Cleaning devices removing liquids removing lubricants

Definitions

  • the present invention relates to a method for degreasing a cold-rolled metal strip, and more particularly a continuously treated strip, preferably a ferrous strip, or a copper strip.
  • the atmosphere used is constituted by a mixture of N 2 , H 2 , H 2 0, C0 2 , and CO, and it results from a sub-stoichiometric combustion of a fossil fuel (gas or fuel ).
  • Total degreasing of the metal strip is therefore obtained by heating and cracking the oils, by chemical action of the gases in the atmosphere of the fumes from the combustion of this fossil fuel.
  • the atmosphere having the composition specified in the prior patent therefore comprises reducing gases (H 2 and CO), and also oxidizing gases (H 2 0 and C0 2 ).
  • N Z -H 2 -H 2 0 mixture comprising a single reducing gas and a single oxidizing gas, of a particular composition, gives the same effects as a mixture with two components of each kind.
  • the present invention relates to a method of degreasing a cold-rolled strip, according to which the degreasing is carried out at the same time as the heating of the strip, by chemical effect at high temperature of an atmosphere of suitable composition, on the oil layer present on the strip, in an enclosure provided with means for supplying heat by radiation, in which the heating and degreasing actions are carried out separately and independently, characterized in that said atmosphere consists essentially of a mixture of nitrogen and hydrogen enriched in water vapor injected into said degreasing section in which the hydrogen content is between 2 and 30% and the water vapor content is between 5 and 30% of the gas mixture filling the enclosure.
  • the metal strip can be brought, by the radiant heating means, to a temperature between 350 and 700 ° C., necessary for carrying out degreasing by chemical effect of the atmosphere.
  • the injected gas mixture can be preheated to a temperature of the order of 700 ° C, by any suitable means.
  • the water vapor from the atmosphere can be injected into a stream N 2 , H 2 (mixture of nitrogen and hydrogen) already preheated .
  • the atmosphere is produced by injecting air in an amount such that the combination of the oxygen contained in the air with the hydrogen present in said atmosphere gives the same final composition of atmospheric gases which if a mixture of nitrogen, hydrogen and water vapor was injected directly, as described above.
  • the injected air supplies the nitrogen of the final composition of the atmosphere, and the water vapor necessary for this final atmosphere results from the combustion of part of the hydrogen of l atmosphere in the presence of oxygen from the air.
  • the degreasing atmosphere is obtained by an injection of air, as specified above, combined with an injection of fumes from the combustion of a gaseous fuel, this combustion being able to be carried out either inside or outside the enclosure where degreasing takes place.
  • the combustion of the gaseous fuel is preferably a sub-stoichiometric combustion, in premix or not, with a rate of unburnt of between 0.5 and 10%.
  • This variant provides a simplification of implementation compared to the process described above, while allowing the same oxidation potential with respect to the strip, since the final composition of the degreasing atmosphere remains the even.
  • an N 2 + H 2 mixture flow rate of 150 Nm 3 / h is injected in the vicinity of the metallization bath. This flow passes through the cooling and annealing sections, and reaches the degreasing section.
  • the atmosphere is produced by injecting oxidizing fumes in an amount such that the excess oxygen contained in the fumes combines with the hydrogen present in the atmosphere to produce water vapor which is added to the water vapor already present in the injected fumes.
  • the degreasing atmosphere thus produced contains hydrogen, water vapor, and a small amount of C0 2 introduced with the fumes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Strip Materials And Filament Materials (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Description

La présente invention est relative à un procédé de dégraissage d'une bande métallique laminée à froid, et plus particulièrement d'une bande traitée en continu, de préférence une bande ferreuse, ou une bande de cuivre.The present invention relates to a method for degreasing a cold-rolled metal strip, and more particularly a continuously treated strip, preferably a ferrous strip, or a copper strip.

Cette invention constitue un perfectionnement de celle décrite et revendiquée dans le brevet européen N° 00 69 009, déposé le 22 juin 1982 par la présente titulaire. Dans ce brevet antérieur, on a décrit un procédé de dégraissage d'une bande métallique laminée à froid dans lequel les actions chauffage et dégraissage sont séparées, c'est-à-dire que quels que soient les besoins de chauffage, le dégraissage est réalisé de façon indépendante.

  • a) le chauffage est effectué dans une enceinte pourvue de moyens d'apport de chaleur par rayonnement, notamment électriques;
  • b) le dégraissage est obtenu par effet d'une atmosphère appropriée dans cette enceinte de chauffage.
This invention constitutes an improvement on that described and claimed in European patent N ° 00 69 009, filed on June 22, 1982 by the present owner. In this prior patent, a method of degreasing a cold-rolled metal strip has been described in which the heating and degreasing actions are separate, that is to say that whatever the heating requirements, degreasing is carried out independently.
  • a) the heating is carried out in an enclosure provided with means for supplying heat by radiation, in particular electrical;
  • b) degreasing is obtained by the effect of an appropriate atmosphere in this heating enclosure.

Dans ce brevet antérieur, l'atmosphère utilisée est constituée par un mélange de N2, H2, H20, C02, et CO, et elle résulte d'une combustion sous-stoechiométrique d'un combustible fossile (gaz ou fuel). Le dégraissage total de la bande métallique est donc obtenu par chauffage et craquage des huiles, par action chimique des gaz de l'atmosphère des fumées issus de la combustion de ce combustible fossile.In this prior patent, the atmosphere used is constituted by a mixture of N 2 , H 2 , H 2 0, C0 2 , and CO, and it results from a sub-stoichiometric combustion of a fossil fuel (gas or fuel ). Total degreasing of the metal strip is therefore obtained by heating and cracking the oils, by chemical action of the gases in the atmosphere of the fumes from the combustion of this fossil fuel.

L'atmosphère ayant la composition précisée dans le brevet antérieur comporte donc des gaz réducteurs (H2 et CO), et également des gaz oxydants (H20 et C02).The atmosphere having the composition specified in the prior patent therefore comprises reducing gases (H 2 and CO), and also oxidizing gases (H 2 0 and C0 2 ).

La demanderesse a constaté qu'un mélange NZ-H2-H20, comportant un seul gaz réducteur et un seul gaz oxydant, d'une composition particulière, procurait les mêmes effets qu'un mélange avec deux composants de chaque nature.The Applicant has found that an N Z -H 2 -H 2 0 mixture, comprising a single reducing gas and a single oxidizing gas, of a particular composition, gives the same effects as a mixture with two components of each kind.

En conséquence, la présente invention concerne un procédé de dégraissage d'une bande laminée à froid, selon lequel le dégraissage est effectué en même temps que le chauffage de la bande, par effet chimique à haute température d'une atmosphère de composition appropriée, sur la couche d'huile présente sur la bande, dans une enceinte pourvue de moyens d'apport de chaleur par rayonnement, dans laquelle les actions de chauffage et dégraissage sont réalisés de façon séparée et indépendante, caractérisé en ce que ladite atmosphère est constituée essentiellement par un mélange d'azote et d'hydrogène enrichi en vapeur d'eau injecté dans ladite section de dégraissage dans lequel la teneur en hydrogène est comprise entre 2 et 30% et la teneur en vapeur d'eau est comprise entre 5 et 30% du mélange gazeux remplissant l'enceinte.Consequently, the present invention relates to a method of degreasing a cold-rolled strip, according to which the degreasing is carried out at the same time as the heating of the strip, by chemical effect at high temperature of an atmosphere of suitable composition, on the oil layer present on the strip, in an enclosure provided with means for supplying heat by radiation, in which the heating and degreasing actions are carried out separately and independently, characterized in that said atmosphere consists essentially of a mixture of nitrogen and hydrogen enriched in water vapor injected into said degreasing section in which the hydrogen content is between 2 and 30% and the water vapor content is between 5 and 30% of the gas mixture filling the enclosure.

Les autres conditions du traitement, spécifiées dans le brevet antérieur, demeurent inchangées.The other processing conditions, specified in the previous patent, remain unchanged.

Selon une caractéristique de cette invention, la bande métallique peut être portée, par les moyens de chauffage par rayonnement, à une température comprise entre 350 et 700°C, nécessaire à la réalisation du dégraissage par effet chimique de l'atmosphère.According to a characteristic of this invention, the metal strip can be brought, by the radiant heating means, to a temperature between 350 and 700 ° C., necessary for carrying out degreasing by chemical effect of the atmosphere.

Pour accroître l'effet chimique de l'atmosphère, le mélange gazeux injecté peut être pré-chauffé jusqu'à une température de l'ordre de 700°C, par tous moyens appropriés.To increase the chemical effect of the atmosphere, the injected gas mixture can be preheated to a temperature of the order of 700 ° C, by any suitable means.

Selon l'invention, pour éviter toute condensation de la vapeur d'eau dans l'enceinte de dégraissage, la vapeur d'eau de l'atmosphère peut être injectée dans un courant N2, H2 (mélange azote et hydrogène) déjà préchauffé.According to the invention, to avoid any condensation of the water vapor in the degreasing enclosure, the water vapor from the atmosphere can be injected into a stream N 2 , H 2 (mixture of nitrogen and hydrogen) already preheated .

La lecture de la description qui précède montre que cette invention apporte un procédé simplifié par rapport au procédé décrit dans le brevet européen N° 00 69 009, le remplacement des gaz de combustion, constitués de N2, H2, CO, C02 et H20, par un mélange de N2, H2 et de vapeur d'eau, injecté au même niveau que dans le procédé antérieur, ou même dans la zone de température plus basse, permettant d'obtenir le même potentiel d'oxydation vis-à-vis de la bande que les fumées de l'atmosphère du brevet antérieur.Reading the above description shows that this invention provides a simplified process compared to the process described in European Patent No. 00 69 009, the replacement of combustion gases, consisting of N 2 , H 2 , CO, C0 2 and H 2 0, by a mixture of N 2 , H 2 and water vapor, injected at the same level as in the previous process, or even in the lower temperature zone, making it possible to obtain the same oxidation potential vis-à-vis the band that the atmospheric fumes of the prior patent.

Selon une variante de cette invention, on peut envisager une mise en oeuvre différente de l'atmosphère de dégraissage.According to a variant of this invention, it is possible to envisage a different implementation of the degreasing atmosphere.

Selon cette variante, l'atmosphère est réalisée par injection d'air en une quantité telle que la combinaison de l'oxygène contenu dans l'air avec l'hydrogène présent dans ladite atmosphère donne la même composition finale de gaz d'atmosphère qui si un mélange d'azote, d'hydrogène et de vapeur d'eau était injecté directement, comme décrit ci-dessus.According to this variant, the atmosphere is produced by injecting air in an amount such that the combination of the oxygen contained in the air with the hydrogen present in said atmosphere gives the same final composition of atmospheric gases which if a mixture of nitrogen, hydrogen and water vapor was injected directly, as described above.

On comprend que, selon cette variante, l'air injecté fournit l'azote de la composition finale de l'atmosphère, et la vapeur d'eau nécessaire à cette atmosphère finale résulte de la combustion d'une partie de l'hydrogène de l'atmosphère en présence de l'oxygène de l'air.It is understood that, according to this variant, the injected air supplies the nitrogen of the final composition of the atmosphere, and the water vapor necessary for this final atmosphere results from the combustion of part of the hydrogen of l atmosphere in the presence of oxygen from the air.

Les autres conditions du traitement spécifiées ci-dessus demeurent inchangées.The other processing conditions specified above remain unchanged.

Selon une autre caractéristique de cette variante, l'atmosphère de dégraissage est obtenue par une injection d'air, comme précisé ci-dessus, combinée avec une injection de fumées issues de la combustion d'un combustible gazeux, cette combustion pouvant être réalisée soit à l'intérieur, soit à l'extérieur de l'enceinte où s'effectue le dégraissage. La combustion du combustible gazeux est de préférence une combustion sous-stoechiométrique, en pré-mélange ou non, avec un taux d'imbrûlés compris entre 0,5 et 10%.According to another characteristic of this variant, the degreasing atmosphere is obtained by an injection of air, as specified above, combined with an injection of fumes from the combustion of a gaseous fuel, this combustion being able to be carried out either inside or outside the enclosure where degreasing takes place. The combustion of the gaseous fuel is preferably a sub-stoichiometric combustion, in premix or not, with a rate of unburnt of between 0.5 and 10%.

Cette variante apporte une simplification de mise en oeuvre par rapport au procédé décrit ci-dessus, tout en permettant le même potentiel d'oxydation vis-à-vis de la bande, étant donné que la composition finale de l'atmosphère de dégraissage demeure la même.This variant provides a simplification of implementation compared to the process described above, while allowing the same oxidation potential with respect to the strip, since the final composition of the degreasing atmosphere remains the even.

On a donné ci-après un exemple de mise en oeuvre du procédé selon cette variante. Le schéma'annexé illustre les étapes du procédé ainsi mis en oeuvre.An example of implementation of the method according to this variant has been given below. The attached diagram illustrates the steps of the process thus implemented.

Dans les conditions typiques d'application du procédé, on injecte un débit de mélange N2+H2 de 150 Nm3/h au voisinage du bain de métallisation. Ce débit traverse les sections de refroidissement et de recuit, et atteint la section de dégraissage.Under the typical conditions of application of the process, an N 2 + H 2 mixture flow rate of 150 Nm 3 / h is injected in the vicinity of the metallization bath. This flow passes through the cooling and annealing sections, and reaches the degreasing section.

On injecte, dans cette section de dégraissage, un débit d'air de 35 Nm3/h. L'oxygène contenu dans l'air se combine avec de l'hydrogène contenu dans ce gaz de balayage, et l'atmosphère qui en résulte contient 4,4% de H2, 8,3% de H20, le reste étant constitué par le l'azote.An air flow rate of 35 Nm 3 / h is injected into this degreasing section. The oxygen in the air combines with hydrogen in this sweeping gas, and the resulting atmosphere contains 4.4% H 2 , 8.3% H 2 0, the rest being consisting of nitrogen.

Le débit total de cette atmosphère étant de 178 Nm3/h, cette opération est équivalente à l'injection, dans la section de la préchauffe, de 361 Nm3/h d'un mélange contenant 11,7% H20 et 88,3% N2.The total flow rate of this atmosphere being 178 Nm 3 / h, this operation is equivalent to injecting, into the preheating section, 361 Nm 3 / h of a mixture containing 11.7% H 2 0 and 88 , 3% N 2 .

Le tableau ci-après résume les conditions de fonctionnement. (cas 1 et Cas 2).The table below summarizes the operating conditions. (case 1 and case 2).

Selon une autre variante de cette invention, l'atmosphère est réalisée par injection des fumées oxydantes selon une quantité telle que l'oxygène excédentaire contenu dans les fumées se combine avec l'hydrogène présent dans l'atmosphère pour produire de la vapeur d'eau qui s'additionne à la vapeur d'eau déjà présente dans les fumées injectées. L'atmosphère de dégraissage ainsi réalisée contient de l'hydrogène, de la vapeur d'eau, et une faible quantité de C02 introduit avec les fumées. Les conditions de fonctionnement sont résumées dans le tableau (cas 3).

Figure imgb0001
According to another variant of this invention, the atmosphere is produced by injecting oxidizing fumes in an amount such that the excess oxygen contained in the fumes combines with the hydrogen present in the atmosphere to produce water vapor which is added to the water vapor already present in the injected fumes. The degreasing atmosphere thus produced contains hydrogen, water vapor, and a small amount of C0 2 introduced with the fumes. The operating conditions are summarized in the table (case 3).
Figure imgb0001

Claims (8)

1. A method of degreasing a cold-rolled strip, according to which the degreasing is carried out at the same time as the heating of the strip, by chemical effect at high temperature of an atmosphere of suitable composition upon the oil layer present on the strip, in an enclosure equipped with means for applying heat by radiation, in which the actions of heating and degreasing are carried out in separate and independent manner, characterized in that said atmosphere is constituted essentially of a mixture of nitrogen and hydrogen enriched with steam, injected into said degreasing section, in which the hydrogen content is from 2 to 30% and the steam content is from 5 to 30% of the gaseous mixture filling the enclosure.
2. A method according to Claim 1, characterized in that the strip is raised by said radiation heating to a temperature of from 350 to 700°C..
3. A method according to any one of Claims 1 or 2, characterized in that the gaseous mixture injected into the degreasing section of the enclosure is subjected to a preheating up to a temperature of the order of 700°C.
4. A method according to any one of the preceding Claims, characterized in that the steam necessary for the degreasing atmosphere is injected into an already preheated flow of the gaseous mixture of nitrogen and hydrogen.
5. A method according to Claim 1, characterized in that the degreasing atmosphere is obtained by injecting air in a quantity such that the combination of the oxygen contained in the air with the hydrogen present in the atmosphere gives the same final composition of atmosphere gas as if a mixture of nitrogen, hydrogen and steam were directly injected.
6. A method according to Claim 5, characterized in that there are also injected, into the degreasing atmosphere, smoke gases issuing from the combustion of a gaseous fuel, carried out either inside or outside the degreasing enclosure.
7. A method according to Claim 5, characterized in that a sub-stoichiometric combustion is used, in premixing or not, with a proportion of unburnt substances of from 0.5 to 10%.
8. A method according to Claim 1, characterized in that the degreasing atmosphere is obtained by injection of oxidizing smoke gases in a quantity such that the excess oxygen contained in the smoke gases combines with the hydrogen present in said atmosphere, producing steam which becomes added to the steam already present in the injected smoke gases, the degreasing atmosphere thus produced containing hydrogen, steam, nitrogen and a small quantity of CO2 introduced with the smoke gases.
EP85400669A 1984-04-05 1985-04-03 Degreasing process for cold-rolled metal strip Expired - Lifetime EP0157708B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85400669T ATE57396T1 (en) 1984-04-05 1985-04-03 DEGREASING PROCESS FOR COLD ROLLED STEEL STRIP.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
FR8405366A FR2562563B1 (en) 1984-04-05 1984-04-05 PROCESS FOR DEGREASING A COLD-ROLLED METAL STRIP
FR8405366 1984-04-05
FR8414950A FR2571064B2 (en) 1984-09-28 1984-09-28 PROCESS FOR DEGREASING A COLD-ROLLED METAL STRIP
FR8414950 1984-09-28

Publications (3)

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EP0157708A2 EP0157708A2 (en) 1985-10-09
EP0157708A3 EP0157708A3 (en) 1987-05-20
EP0157708B1 true EP0157708B1 (en) 1990-10-10

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CA1314451C (en) * 1987-06-05 1993-03-16 James E. Heath Cleaning unit
GB8827933D0 (en) * 1988-11-30 1989-01-05 Plessey Co Plc Improvements relating to soldering processes
EP0506175B1 (en) * 1991-03-26 1996-12-04 Koninklijke Philips Electronics N.V. Liquid crystal display device comprising an orientation layer
GB2274286B (en) * 1993-01-13 1996-11-06 Singapore Asahi Chemical & Solder Ind Pte Ltd Method of and apparatus for preparing an electric circuit board for a flow or wave soldering process
US5578147A (en) * 1995-05-12 1996-11-26 The Boc Group, Inc. Controlled process for the heat treating of delubed material
DE19840778A1 (en) * 1998-09-07 2000-03-09 Messer Griesheim Gmbh Method and device for cleaning metal surfaces
JP6367402B1 (en) * 2017-02-28 2018-08-01 モリテックスチール株式会社 Oil removal system using superheated steam and superheated steam generator

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US2625495A (en) * 1948-06-04 1953-01-13 Surface Combustion Corp High-temperature cleaning of ferrous metal
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FR2415147A1 (en) * 1978-01-19 1979-08-17 Valjim Corp Direct current electrical heat treatment of continuous metal band - in protective atmosphere contg. small amounts of reacting gases
CA1152870A (en) * 1979-12-24 1983-08-30 Hiromitsu Naito Process for continuously annealing of a cold rolled steel strip
FR2508064B1 (en) * 1981-06-23 1987-07-10 Stein Heurtey PROCESS FOR DEGREASING A COLD ROLLED BELT
FR2562562B1 (en) * 1984-04-04 1986-08-08 Stein Heurtey METHOD AND DEVICE FOR CONTINUOUS CLEANING OF A METAL STRIP

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EP0157708A3 (en) 1987-05-20
US4840680A (en) 1989-06-20
EP0157708A2 (en) 1985-10-09
DE3580055D1 (en) 1990-11-15

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