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EP0061411A1 - Process for precisely and continuously injecting a gaseous halide compound into a liquid metal - Google Patents

Process for precisely and continuously injecting a gaseous halide compound into a liquid metal Download PDF

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Publication number
EP0061411A1
EP0061411A1 EP82420037A EP82420037A EP0061411A1 EP 0061411 A1 EP0061411 A1 EP 0061411A1 EP 82420037 A EP82420037 A EP 82420037A EP 82420037 A EP82420037 A EP 82420037A EP 0061411 A1 EP0061411 A1 EP 0061411A1
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EP
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Prior art keywords
injection
halogenated
liquid metal
vaporizer
ccl
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EP82420037A
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German (de)
French (fr)
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EP0061411B1 (en
Inventor
Gilbert Pollet
Pierre Du Manoir
Pierre Guerit
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Servimetal SA
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Servimetal SA
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B21/00—Obtaining aluminium
    • C22B21/06—Obtaining aluminium refining
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B21/00—Obtaining aluminium
    • C22B21/06—Obtaining aluminium refining
    • C22B21/064—Obtaining aluminium refining using inert or reactive gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D21/00—Casting non-ferrous metals or metallic compounds so far as their metallurgical properties are of importance for the casting procedure; Selection of compositions therefor
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/05—Refining by treating with gases, e.g. gas flushing also refining by means of a material generating gas in situ

Definitions

  • the present invention relates to a method and an apparatus for the precise injection, into a liquid metal, of halogenated derivatives, liquid or in solution.
  • the present invention belongs to this second category. Indeed, the handling and use of chlorine in foundry workshops poses safety, hygiene, pollution and corrosion problems which encourage us to seek other solutions.
  • anhydrous metal chlorides such as TiCl 4 , A1C1 3 , MnCl2, and organic derivatives such as CCl 4 (carbon tetrachloride), C 2 Cl 4 (perchlorethylene) or C 2 Cl 6 were used ( hexachloroethane).
  • This product which is solid at ordinary temperature, sublimes around 187 ° C. For this reason, it is usually introduced into aluminum in the form of pellets arranged in a chamber through which the liquid metal passes, or, by means of '' a perforated bell, made of graphite, which is lowered into the liquid metal.
  • its volatilization and thermal cracking are extremely rapid and require little more than 2 to 3 minutes. But this speed excludes any possibility of precise dosing and, above all, of continuous action on a stream of liquid aluminum.
  • the doses used are much greater than the quantity actually necessary, the excess requires effective capture.
  • the invention is based on the use of a halogenated substance which is liquid at room temperature and has an Cl / C atomic ratio at least equal to 2 and preferably between 2 and 4.
  • the process which is the subject of the invention consists in taking the halogenated substance or the halogenated solution, liquid at room temperature, in introducing it, by means of a metering micropump, into a vaporizer brought to a temperature such as the substance is brought to a temperature higher than its vaporization temperature and to inject the vapor, under the action of a current of inert gas, into the liquid metal to be treated.
  • halogenated substance a defined chemical species, or a mixture of defined chemical species, composed of carbon and at least one halogen chosen from chlorine and fluorine.
  • the apparatus for implementing the process comprises a reservoir of liquid halogenated substance, a micro metering pump, a reactor provided with a heating means, a source of inert pressurized gas, provided with a means for adjusting the pressure and flow, and a means of injection into the liquid metal to be treated.
  • Figure 1 shows schematically the apparatus. It consists of: a tank (1) fitted with a tight cover (2), a closable nozzle (3) for filling, a level gauge (4); a sampling tube (5), fitted with a shut-off valve (6), is connected to a piston metering micropump (7) which can collect and precisely inject the halogenated substance (8), to a rate which can be, for example, between 0.1 and 10 milliliters per minute, without these values constituting a limitation of the invention.
  • the liquid halogenated substance (8) passes through a non-return valve (9) and enters the vaporizer (10) provided with a regulated and thermostatically controlled heating means (11), of any known type, for example with electrical resistance.
  • An inert gas such as nitrogen, argon or helium, taken from the pressurized storage means (12) using a pressure reducer (13) and a flow meter (14), also enters the reactor where it mixes with the vapors. of the halogenated substance and drives them, via the injection pipe (15) to the injection means (16) which can be, for example, a graphite rod, immersed in the liquid metal (17) passing through the treatment (18).
  • a variant of the device, for higher treatment gas flow rates consists in adding to the system described above, an additional flow of gas: nitrogen, argon or helium, introduced downstream of the vaporizer (10) by a nozzle. (24) on the pipe (15); this allows, in the operating range of the micro-pump, to ensure the desired amount of halogen with a predetermined dilution level without passing the entire gas flow through the vaporizer.
  • This solution has the advantage of a higher chlorine content by weight than that of pure C 2 C1 4 , while retaining the advantage of the liquid state, which allows its precise injection by a metering pump. If you want to keep the mixture its liquid state at temperatures close to ambient, you can introduce up to about 500 grams / liter of C 2 Cl 6 .
  • the halogenated substance may also consist, partially or wholly, of chlorofluorinated derivatives, and in particular CC1 3 F, CCl 3 -CF 3 , CCl 2 F-CClF 2 , CCl 3 -CClF 2 , CC1 2 F-CC1 2 F , CCl 3 -CCl 2 F, whose boiling points range from 24 to 138 ° C.
  • the injection pump is a positive displacement piston pump designed to deliver precisely small volumes of predetermined liquid and with a reliability of ⁇ 1% by volume.
  • a diaphragm pump could also be used.
  • the vaporizer preferably comprises a spiral tube or a bundle of parallel tubes, so that the halogenated substance and the carrier gas can exit therefrom at a temperature which can reach 200 ° C. and even beyond, if this is necessary, but sufficient to avoid any condensation and which must be adapted to the halogenated derivative chosen and to the pressure under which the injection is carried out.
  • the heating is ensured by an electric resistance regulated from a temperature sensor arranged on the path of the gases leaving the. spray.
  • the injection into the liquid metal can be carried out by various known means, for example, by a graphite rod (16) disposed in the upstream compartment (19) of the treatment bag (18) into which the metal to be purified arrives or by a porous plug (20) placed at the bottom of the pocket according to a well-known technique (French patent FR No. 1,031,504).
  • the downstream compartment (21) is separated from the upstream compartment by a partition (22) and it may include any known filtration means such as alumina beads or granules (23).
  • the injection can also be carried out in rotary devices such as the "Spinning Nozzle Inert flotation System” (SNIF) of UNION CARBIDE (US patent 3,870,511) as a replacement for the injection of chlorine, or in devices similar to propeller or turbine, in which the arrival of the halogenated vapors and the carrier gas is done by the axis.
  • rotary devices such as the "Spinning Nozzle Inert flotation System” (SNIF) of UNION CARBIDE (US patent 3,870,511) as a replacement for the injection of chlorine, or in devices similar to propeller or turbine, in which the arrival of the halogenated vapors and the carrier gas is done by the axis.
  • the metal is continuously treated in passing, by injection of the halogenated substance. But he is not contrary to the invention to treat, in the same way, successive metal charges in a crucible or in a basin furnace.
  • An injection device was constructed, according to the diagram in FIG. 1, comprising a 10-liter reservoir, of a mixture at 80% by weight of perchlorethylene and 20% by weight of hexachloroethane.
  • the dosing micropump has an adjustable flow rate between 1 and 10 milliliters / minute.
  • the vaporizer is preheated to (280 ⁇ 5 ° C).
  • the carrier gas is nitrogen, injected at a pressure of 2.5 bars and a flow rate of 2 m3 / hour.
  • the amount of perchlorethylene-hexachlorethane mixture was adjusted to 250 milliliters / hour corresponding to 100 grams of chlorine for a flow rate of aluminum, in the treatment bag, of 2 tonnes / hour.

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Abstract

The invention relates to a process and an apparatus for the precise and continuous injection of a halogenated derivative, which is liquid at ambient temperature, into a liquid metal such as aluminum and aluminum-based alloys. The process involves withdrawing the halogenated substance from a tank, introducing it by means of a metering pump into a vaporizer which has been brought to a temperature at least equal to the vaporization temperature of the substance under the injection pressure, and entraining it in the vapor state by an inert gas stream towards an injection means opening into the center of the liquid metal.

Description

La présente invention concerne un procédé et un appareillage pour l'injection précise, dans un métal liquide, de dérivés halogénés liquides ou en solution.The present invention relates to a method and an apparatus for the precise injection, into a liquid metal, of halogenated derivatives, liquid or in solution.

Elle est principalement destinée à l'injection précise de quantités prédéterminées de dérivés halogénés liquides dans l'aluminium et les alliages à base d'aluminium.It is mainly intended for the precise injection of predetermined quantities of halogenated liquid derivatives into aluminum and aluminum-based alloys.

Il est connu que l'aluminium et certains alliages à base d'aluminium doivent, avant leur mise en forme, subir un traitement de purification ayant notamment pour but d'en expulser les gaz occlus, d'en éliminer certains composants indésirables - tels que le sodium - et de faciliter le rassemblement en surface des inclusions d'alumine ou autres oxydes.It is known that aluminum and certain aluminum-based alloys must, before their shaping, undergo a purification treatment having in particular the aim of expelling the occluded gases therefrom, of eliminating certain undesirable components from it - such as sodium - and to facilitate the gathering on the surface of inclusions of alumina or other oxides.

Ce traitement de purification peut être mis en oeuvre par des procédés différents, mais qui se classent en deux catégories :

  • - l'injection de chlore gazeux, pur ou dilué dans un gaz inerte (azote, argon) par tout myen connu tel que canne en graphite plongée dans le métal liquide, bouchon poreux disposé au fond d'une poche, etc...
  • - l'injection d'un dérivé halogéné, dont la décomposition à la température du métal liquide libère du chlore actif.
This purification treatment can be carried out by different methods, but which fall into two categories:
  • - injection of chlorine gas, pure or diluted in an inert gas (nitrogen, argon) by any known myen such as graphite cane immersed in liquid metal, porous plug placed at the bottom of a pocket, etc ...
  • - the injection of a halogenated derivative, the decomposition of which at the temperature of the liquid metal releases active chlorine.

La présente invention appartient à cette deuxième catégorie. En effet, la manipulation et l'utilisation du chlore dans les ateliers de fonderie pose des problèmes de sécurité, d'hygiène, de pollution et de corrosion qui incitent à chercher d'autres solutions.The present invention belongs to this second category. Indeed, the handling and use of chlorine in foundry workshops poses safety, hygiene, pollution and corrosion problems which encourage us to seek other solutions.

Parmi les dérivés halogénés, on a utilisé des chlorures métalliques anhydres, tels que TiCl4, A1C13, MnCl2, et des dérivés organiques tels que CCl4 (tétrachlorure de carbone), C2Cl4 (perchloréthylène) ou C2Cl6 (hexachloréthane).Among the halogenated derivatives, anhydrous metal chlorides, such as TiCl 4 , A1C1 3 , MnCl2, and organic derivatives such as CCl 4 (carbon tetrachloride), C 2 Cl 4 (perchlorethylene) or C 2 Cl 6 were used ( hexachloroethane).

Ces procédés ont été décrits, en particulier. dans "Aluminium, Tome 1, Péchiney, Editions Eyrolles, Paris 1964, pages 527-528; dans Aluminum, Kent R. Van Horn, Tome III, American Society of Metals 1967, pages 31-32; dans "Aluminium Taschenbuch" 13, Edition 1974, pages 373-375.These methods have been described, in particular. in "Aluminum, Tome 1, Péchiney, Editions Eyrolles, Paris 1964, pages 527-528; in Aluminum, Kent R. Van Horn, Tome III, American Society of Metals 1967, pages 31-32; in "Aluminum Taschenbuch" 13, Edition 1974, pages 373-375.

L'utilisation de l'hexachloréthane a également été décrite dans les brevets GB. 603 213 et 827 619 au nom de FOSECO.The use of hexachloroethane has also been described in the GB patents. 603 213 and 827 619 in the name of FOSECO.

Ce produit, qui est solide à la température ordinaire, se sublime vers 187° C. Pour cette raison, on l'introduit habituellement dans l'aluminium sous forme de pastilles disposées dans une chambre que traverse le métal liquide, ou, au moyen d'une cloche perforée, en graphite, que l'on fait descendre, dans le métal liquide. De ce fait, sa volatilisation et son craquage thermique sont extrêmement rapides et ne demandent guère plus de 2 à 3 minutes. Mais cette rapidité exclut toute possibilité de dosage précis et, surtout d'action continue sur un courant d'aluminium liquide. En outre, les doses utilisées étant très supérieures à la quantité réellement nécessaire, l'excès nécessite une captation efficace.This product, which is solid at ordinary temperature, sublimes around 187 ° C. For this reason, it is usually introduced into aluminum in the form of pellets arranged in a chamber through which the liquid metal passes, or, by means of '' a perforated bell, made of graphite, which is lowered into the liquid metal. As a result, its volatilization and thermal cracking are extremely rapid and require little more than 2 to 3 minutes. But this speed excludes any possibility of precise dosing and, above all, of continuous action on a stream of liquid aluminum. In addition, since the doses used are much greater than the quantity actually necessary, the excess requires effective capture.

L'invention est basée sur l'utilisation d'une substance halogénée liquide à la température ambiante et ayant un rapport atomique Cl/C au moins égal à 2 et, de préférence, compris entre 2 et 4.The invention is based on the use of a halogenated substance which is liquid at room temperature and has an Cl / C atomic ratio at least equal to 2 and preferably between 2 and 4.

Le procédé, objet de l'invention, consiste à prendre la substance halo- gênée ou la solution halogénée, liquide à la température ambiante, a l'introduire, au moyen d'une micropompe doseuse, dans un vaporisateur porté à une température telle que la substance soit amenée à une tempé-rature supérieure à sa température de vaporisation et à injecter la vapeur, sous l'action d'un courant de gaz inerte, dans le métal liquide à traiter.The process which is the subject of the invention consists in taking the halogenated substance or the halogenated solution, liquid at room temperature, in introducing it, by means of a metering micropump, into a vaporizer brought to a temperature such as the substance is brought to a temperature higher than its vaporization temperature and to inject the vapor, under the action of a current of inert gas, into the liquid metal to be treated.

Dans tout ce qui suit, nous désignerons par le terme "substance halogénée" une espèce chimique définie, ou un mélange d'espèces chimiques définies, composée de carbone et d'au moins un halogène choisi parmi le chlore et le fluor.In all that follows, we will denote by the term "halogenated substance" a defined chemical species, or a mixture of defined chemical species, composed of carbon and at least one halogen chosen from chlorine and fluorine.

L'appareillage pour la mise en oeuvre du procédé comporte un réservoir de substance halogénée liquide, une micro pompe doseuse, un réacteur muni d'un moyen de chauffage, une source de gaz inerte sous pression, munie d'un moyen de réglage de la pression et du débit, et d'un moyen d'injection dans le métal liquide à traiter.The apparatus for implementing the process comprises a reservoir of liquid halogenated substance, a micro metering pump, a reactor provided with a heating means, a source of inert pressurized gas, provided with a means for adjusting the pressure and flow, and a means of injection into the liquid metal to be treated.

La figure 1 schématise l'appareillage. Il se compose : d'un réservoir (1) muni d'un couvercle étanche (2), d'un ajutage obturable (3) pour procéder au remplissage, d'une jauge de niveau (4); un tube de prélèvement (5), muni d'une vanne d'arrêt (6), est relié à une micropompe doseuse à piston (7) qui peut prélever et injecter, de façon précise, la substance halogénée (8), à une cadence qui peut se situer, par exemple, entre 0,1 et 10 millilitres par minute, sans que ces valeurs constituent une limitation de l'invention.Figure 1 shows schematically the apparatus. It consists of: a tank (1) fitted with a tight cover (2), a closable nozzle (3) for filling, a level gauge (4); a sampling tube (5), fitted with a shut-off valve (6), is connected to a piston metering micropump (7) which can collect and precisely inject the halogenated substance (8), to a rate which can be, for example, between 0.1 and 10 milliliters per minute, without these values constituting a limitation of the invention.

La substance halogénée liquide (8) franchit un clapet antiretour (9) et pénètre dans le vaporisateur (10) muni d'un moyen de chauffage (11) régulé et thermostaté, de tout type connu, par exemple à résistance électrique.The liquid halogenated substance (8) passes through a non-return valve (9) and enters the vaporizer (10) provided with a regulated and thermostatically controlled heating means (11), of any known type, for example with electrical resistance.

Un gaz inerte, tel qu'azote, argon ou hélium, prélevé dans le moyen de stockage sous pression (12) grâce à un détendeur (13) et à un débitmètre (14), pénètre également dans le réacteur où il se mêle aux vapeurs de la substance halogénée et les entraîne, par la canalisation d'injection (15) vers le moyen d'injection (16) qui peut être, par exemple, une canne en graphite, plongé dans le métal liquide (17) traversant la poche de traitement (18).An inert gas, such as nitrogen, argon or helium, taken from the pressurized storage means (12) using a pressure reducer (13) and a flow meter (14), also enters the reactor where it mixes with the vapors. of the halogenated substance and drives them, via the injection pipe (15) to the injection means (16) which can be, for example, a graphite rod, immersed in the liquid metal (17) passing through the treatment (18).

Une variante de l'appareil, pour des débits de gaz de traitement plus importants, consiste à ajouter au système décrit ci-dessus, un débit supplémentaire de gaz : azote, argon ou hélium, introduit en aval du vaporisateur (10) par un piquage (24) sur la canalisation (15); cela permet, dans la plage de fonctionnement de la micro-pompe, d'assurer la quantité d'halogène souhaitée avec un niveau de dilution prédéterminé sans faire passer la totalité du débit gazeux dans le vaporisateur.A variant of the device, for higher treatment gas flow rates, consists in adding to the system described above, an additional flow of gas: nitrogen, argon or helium, introduced downstream of the vaporizer (10) by a nozzle. (24) on the pipe (15); this allows, in the operating range of the micro-pump, to ensure the desired amount of halogen with a predetermined dilution level without passing the entire gas flow through the vaporizer.

Le produit halogéné (8) peut être du perchloréthylène C12C = CCl2, liquide à la température ambiante (PF : - 22°C; PE : + 121°C), avec un rapport atomique Cl/C = 2, et une teneur pondérale en C1 de 74,7 % ou, de préférence, une solution d'hexachloréthane C2C16, solide à la température ambiante, avec un rapport atomique Cl/C = 3 et une teneur pondérale au chlore de 89,9 % dans du perchloréthylène C2Cl4. Cette solution a l'avantage d'une teneur pondérale en chlore plus élevée que celle de C2C14 pur, tout en conservant l'avantage de l'état liquide, qui permet son injection précise par une pompe doseuse. Si l'on veut conserver au mélange son état liquide a des température voisines de l'ambiante, on peut introduire jusqu'à environ 500 grammes/Litre de C2Cl6.The halogenated product (8) can be perchlorethylene C1 2 C = CCl 2 , liquid at room temperature (PF: - 22 ° C; PE: + 121 ° C), with an atomic ratio Cl / C = 2, and a C1 content by weight of 74.7% or, preferably, a solution of hexachlorethane C 2 C1 6 , solid at room temperature, with an atomic ratio Cl / C = 3 and a chlorine weight content of 89.9% in perchlorethylene C 2 Cl 4 . This solution has the advantage of a higher chlorine content by weight than that of pure C 2 C1 4 , while retaining the advantage of the liquid state, which allows its precise injection by a metering pump. If you want to keep the mixture its liquid state at temperatures close to ambient, you can introduce up to about 500 grams / liter of C 2 Cl 6 .

Afin d'éviter les problèmes de cristallisation au stockage, on a choisi une solution contenant de 0,1 à 30 % et, de préférence, de 15 à 20 % en poids de C2Cl6.In order to avoid the problems of crystallization during storage, a solution containing 0.1 to 30% and preferably 15 to 20% by weight of C 2 Cl 6 was chosen.

L'usage du tétrachlorure de carbone CC14, bien que théoriquement attractif, en raison de son rapport Cl/C = 4, et de sa teneur en chlore de 92,2 % est, en pratique, exclu en raison de sa toxicité.The use of carbon tetrachloride CC1 4 , although theoretically attractive, because of its Cl / C ratio = 4, and its chlorine content of 92.2% is, in practice, excluded because of its toxicity.

La substance halogénée peut également être constituée, partiellement ou en totalité, par des dérivés chlorofluorés, et notamment CC13F, CCl3-CF3, CCl2F-CClF2, CCl3-CClF2, CC12F-CC12F, CCl3-CCl2F, dont les points d'ébullition s'échelonnent entre 24 et 138° C.The halogenated substance may also consist, partially or wholly, of chlorofluorinated derivatives, and in particular CC1 3 F, CCl 3 -CF 3 , CCl 2 F-CClF 2 , CCl 3 -CClF 2 , CC1 2 F-CC1 2 F , CCl 3 -CCl 2 F, whose boiling points range from 24 to 138 ° C.

Il est également possible d'ajouter à la substance halogénée certaines additions physiquement et chimiquement compatibles, telles que le tétrachlorure de titane (TiCl4), dont l'effet sur la grosseur de grain de l'aluminium est bien connu ou, éventuellement, du trichlorure de bore (BC13), grâce auquel on peut provoquer l'élimination, sous forme de borures insolubles, des impuretés ayant une influence néfaste sur la conductivité électrique de l'aluminium, telles que le titane, le zirconium, le chrome, le vanadium.It is also possible to add to the halogenated substance certain physically and chemically compatible additions, such as titanium tetrachloride (TiCl 4 ), the effect of which on the grain size of aluminum is well known or, possibly, boron trichloride (BC1 3 ), thanks to which it is possible to cause the elimination, in the form of insoluble borides, of impurities having a detrimental influence on the electrical conductivity of aluminum, such as titanium, zirconium, chromium, vanadium.

La pompe d'injection est une pompe volumétrique à pistons étudiée pour débiter avec précision de faibles volumes de liquide prédéterminé et avec une fiabilité de ± 1 % en volume. Une pompe à membrane pourrait aussi être utilisée.The injection pump is a positive displacement piston pump designed to deliver precisely small volumes of predetermined liquid and with a reliability of ± 1% by volume. A diaphragm pump could also be used.

Le vaporisateur comporte, de préférence, un tube en spirale ou un fais-- ceau de tubes parallèles, de façon que la substance halogénée et le gaz vecteur puissent en ressortir à une température qui peut atteindre 200°C et même au-delà, si c'est nécessaire, mais suffisante pour éviter toute condensation et qui doit être adaptée au dérivé halogéné choisi et à la pression sous laquelle est effectuée l'injection.The vaporizer preferably comprises a spiral tube or a bundle of parallel tubes, so that the halogenated substance and the carrier gas can exit therefrom at a temperature which can reach 200 ° C. and even beyond, if this is necessary, but sufficient to avoid any condensation and which must be adapted to the halogenated derivative chosen and to the pressure under which the injection is carried out.

Le chauffage est assuré par une résistance électrique régulée à partir d'un capteur de température disposé sur le trajet des gaz sortant du. vaporisateur.The heating is ensured by an electric resistance regulated from a temperature sensor arranged on the path of the gases leaving the. spray.

L'injection dans le métal liquide peut être effectuée par différents moyens connus, par exemple, par une canne en graphite (16) disposée dans le compartiment amont (19) de la poche de traitement (18) dans laquelle arrive le métal à purifier ou par un bouchon poreux (20) placé au fond de la poche selon une technique bien connue (brevet français FR n° 1 031 504).The injection into the liquid metal can be carried out by various known means, for example, by a graphite rod (16) disposed in the upstream compartment (19) of the treatment bag (18) into which the metal to be purified arrives or by a porous plug (20) placed at the bottom of the pocket according to a well-known technique (French patent FR No. 1,031,504).

Le compartiment aval (21) est séparé du compartiment amont par une cloison (22) et il peut comporter tout moyen de filtration connu tel que des billes ou granulés d'alumine (23).The downstream compartment (21) is separated from the upstream compartment by a partition (22) and it may include any known filtration means such as alumina beads or granules (23).

L'injection peut également être effectuée dans des dispositifs rotatifs tels que le "Spinning Nozzle Inert flotation System" (SNIF) d'UNION CARBIDE (brevet US 3 870 511) en remplacement de l'injection de chlore, ou dans des dispositfs analogues à hélice ou à turbine, dans lesquels l'arrivée des vapeurs halogénées et du gaz vecteur se fait par l'axe.The injection can also be carried out in rotary devices such as the "Spinning Nozzle Inert flotation System" (SNIF) of UNION CARBIDE (US patent 3,870,511) as a replacement for the injection of chlorine, or in devices similar to propeller or turbine, in which the arrival of the halogenated vapors and the carrier gas is done by the axis.

Il peut être nécessaire de calorifuger la canalisation d'injection (15) lorsqu'elle est relativement longue et que l'on craint qu'une partie du produit vaporisé ne se recondense avant son arrivée dans le dispositif d'injection proprement dit.It may be necessary to insulate the injection pipe (15) when it is relatively long and it is feared that part of the vaporized product will recondense before it arrives in the injection device itself.

Dans le cas représenté sur la figure 1, le métal est traité en continu au passage, par injection de la substance halogénée. Mais il n'est pas contraire à l'invention de traiter,.de la même façon, des charges de métal successives en creuset ou en four à bassin.In the case shown in Figure 1, the metal is continuously treated in passing, by injection of the halogenated substance. But he is not contrary to the invention to treat, in the same way, successive metal charges in a crucible or in a basin furnace.

EXEMPLE D'APPLICATIONAPPLICATION EXAMPLE

On a construit un dispositif d'injection, conforme au schéma de la figure 1, comportant un réservoir de 10 litres, d'un mélange à 80 % en poids de perchloréthylène et de 20 % en poids d'hexachloréthane.An injection device was constructed, according to the diagram in FIG. 1, comprising a 10-liter reservoir, of a mixture at 80% by weight of perchlorethylene and 20% by weight of hexachloroethane.

La micropompe doseuse a un débit réglable entre 1 et 10 millilitres/ minute.The dosing micropump has an adjustable flow rate between 1 and 10 milliliters / minute.

Le vaporisateur est préchauffé à (280 ± 5°C). Le gaz vecteur est de l'azote, injecté sous une pression de 2,5 bars et un débit de 2 m3/ heure.The vaporizer is preheated to (280 ± 5 ° C). The carrier gas is nitrogen, injected at a pressure of 2.5 bars and a flow rate of 2 m3 / hour.

On a ainsi traité, de façon continue, de l'aluminium non allié, de qualité A5 (Al ≥ 99,5 %), destiné à la coulée semi-continue de bandes.There was thus treated, continuously, unalloyed aluminum, of quality A5 (Al ≥ 99.5%), intended for the semi-continuous casting of strips.

La quantité de mélange perchloréthylène-hexachloréthane a été ajustée à 250 millilitres/heure correspondant à 100 grammes de chlore pour un débit d'aluminium, dans la poche de traitement, de 2 tonnes/heure.The amount of perchlorethylene-hexachlorethane mixture was adjusted to 250 milliliters / hour corresponding to 100 grams of chlorine for a flow rate of aluminum, in the treatment bag, of 2 tonnes / hour.

Les tests habituels ont montré que la teneur en hydrogène de l'aluminium coulé était de 0,12 cm3/100 g, équivalent à celle obtenue par un traitement classique par mélange argon-chlore.The usual tests have shown that the hydrogen content of the cast aluminum was 0.12 cm3 / 100 g, equivalent to that obtained by a conventional treatment with an argon-chlorine mixture.

Pendant le traitement, les fumées au-dessus de la poche étaient en quantité très faible ou nulle, et on n'a pas détecté la présence de phosgène même à proximité immédiate de la poche.During treatment, the fumes above the bag were very low or zero, and the presence of phosgene was not detected even in the immediate vicinity of the bag.

Au total, la mise en oeuvre de l'invention présente les avantages suivants :

  • - fonctionnement continu de l'injection, même sur une période de temps prolongée, car on peut regarnir le réservoir de substance halogénée sans interrompre l'injection.
  • - dosage très précis, et réglable à volonté, ce qui écarte tout risque de surdosage et conduit à un rendement en chlore proche de 100 %,
  • - aucun dégagement de produit nocif et pratiquement pas de dégagement de fumées au-dessus de la cuve,
  • - compatibilité avec les moyens et appareillages de traitement de l'aluminium : tels que poches, cannes d'injection, bouchons poreux; avec ou sans utilisation de moyens de filtration ou de couvertures de flux halogéné,
  • - aucun problème pour le stockage de la substance halogénée, qui est stable, ininflammable, non corrosive, et dont la tension de vapeur, relativement basse à la température ambiante, assure un niveau de toxicité très faible.
In total, the implementation of the invention has the following advantages:
  • - continuous operation of the injection, even over an extended period of time, since the reservoir of halogenated substance can be refilled without interrupting the injection.
  • - very precise dosage, and adjustable at will, which eliminates any risk of overdose and leads to a chlorine yield close to 100%,
  • - no release of harmful product and practically no release of smoke above the tank,
  • - compatibility with the means and equipment for processing aluminum: such as bags, injection pipes, porous plugs; with or without the use of filtration means or halogen flux covers,
  • - No problem for the storage of the halogenated substance, which is stable, non-flammable, non-corrosive, and whose vapor pressure, relatively low at room temperature, ensures a very low level of toxicity.

Ce procédé élimine tous les problèmes liés à l'utilisation du chlore gazeux (stockage, dangers de fuite, corrosion, maintenance des installations, traitement des effluents gazeux, etc...)This process eliminates all the problems linked to the use of chlorine gas (storage, risk of leaks, corrosion, maintenance of installations, treatment of gaseous effluents, etc.)

Claims (8)

1/ Procédé d'injection précise et continue dans un métal liquide d'une substance halogénée, liquide à la température ambiante, constituée d'au moins une espèce chimique définie, composée de carbone et d'au moins un halogène choisi parmi le chlore et le fluor, telle que le perchloréthylène, l'hexachlorêthane, le tétrachlorure de carbone et les dérivés chlorofluorés : CCl3, CC13-CF3, CCl2F-CClF2, CCl3-CClF2, CCl2F-CCl2F, CC12 F, caractérisé en ce qu'on prélève ladite substance halogénée dans un réservoir, en ce qu' on l'introduit, au moyen d'une pompe doseuse, dans un vaporisateur porté à une température au moins égale à la température de vaporisation de ladite substance sous la pression d'injection, et en ce qu'on l'entraîne, à l'état de vapeur, par un courant de gaz inerte, vers un moyen d'injection débouchant au sein du métal liquide. -1 / Process for precise and continuous injection into a liquid metal of a halogenated substance, liquid at room temperature, consisting of at least one defined chemical species, composed of carbon and at least one halogen chosen from chlorine and fluorine, such as perchlorethylene, hexachlorethane, carbon tetrachloride and chlorofluorine derivatives: CCl 3 , CC1 3 -CF 3 , CCl 2 F-CClF 2 , CCl 3 -CClF 2 , CCl 2 F-CCl 2 F , CC1 2 F , characterized in that the said halogenated substance is taken from a tank, in that it is introduced, by means of a metering pump, into a vaporizer brought to a temperature at least equal to the temperature of vaporization of said substance under the injection pressure, and in that it is entrained, in the vapor state, by a current of inert gas, towards an injection means opening into the liquid metal. - 2/ Procédé d'injection, selon revendication 1, caractérisé en ce que l'on procède à une introduction supplémentaire de gaz inerte, en aval du vaporisateur.2 / injection method according to claim 1, characterized in that one proceeds to an additional introduction of inert gas, downstream of the vaporizer. 3/ Procédé d'injection, selon revendication 1 ou 2, caractérisé en ce que le moyen d'injection est disposé dans une poche traversée par le courant de métal liquide.3 / Injection method according to claim 1 or 2, characterized in that the injection means is disposed in a pocket through which the stream of liquid metal passes. 4/ Procédé d'injection, selon revendication 1 ou 2, caractérisé en ce que le moyen d'injection est disposé dans un creuset ou dans un four à bassin.4 / Injection method according to claim 1 or 2, characterized in that the injection means is arranged in a crucible or in a basin oven. 5/ Procédé d'injection selon l'une des revendications 1 ou 2, caractérisé en ce que la substance halogénée est constituée par une solution d'he xachloréthane dans du perchloréthylène, à une concentration comprise entre 0,1 et 30 % en poids d'hexachloréthane et, de préférence, comprise entre 15 et 20 %.5 / injection method according to one of claims 1 or 2, characterized in that the halogenated substance consists of a solution of xachlorethane he in perchlorethylene, at a concentration between 0.1 and 30% by weight d hexachlorethane and preferably between 15 and 20%. 6/ Procédé d'injection selon la revendication 5, caractérisé en ce que la substance halogénée peut contenir, en outre, au moins une halogénure métallique anhydre tel que TiCl4 ou BCl3.6 / An injection method according to claim 5, characterized in that the halogenated substance may contain, in addition, at least one anhydrous metal halide such as TiCl 4 or BCl 3 . 7/ Appareillage pour la mise en oeuvre du procédé d'injection précise et continue d'une substance halogénée liquide à la température ambiante dans un métal liquide, selon l'une quelconque des revendications 1 à 6, caractérisé en ce qu'il comporte : un réservoir de produit halogéné (1), relié à l'entrée d'une micropompe doseuse (7), dont la sortie débite sur un vaporisateur (10) muni d'un moyen de chauffage (11) et relié à une source de gaz inerte (12), munie d'un moyen de réglage de pression (13) et de débit (14), et une canalisation de liaison (15) entre le vaporisateur et le moyen d'injection (16) de la substance halogénée.7 / Apparatus for implementing the precise injection process and continuous of a halogenated substance liquid at room temperature in a liquid metal, according to any one of claims 1 to 6, characterized in that it comprises: a reservoir of halogenated product (1), connected to the inlet a metering micropump (7), the output of which flows on a vaporizer (10) provided with a heating means (11) and connected to a source of inert gas (12), provided with a pressure adjustment means (13) and flow (14), and a connecting pipe (15) between the vaporizer and the injection means (16) of the halogenated substance. 8/ Appareillage selon revendication 7, caractérisé en ce qu'il comporte, en outre, un moyen d'introduction supplémentaire (24) de gaz inerte en aval du vaporisateur.8 / Apparatus according to claim 7, characterized in that it further comprises an additional introduction means (24) of inert gas downstream of the vaporizer.
EP82420037A 1981-03-23 1982-03-19 Process for precisely and continuously injecting a gaseous halide compound into a liquid metal Expired EP0061411B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT82420037T ATE20541T1 (en) 1981-03-23 1982-03-19 METHOD OF ACCURATELY AND CONTINUOUSLY INJECTING A GASEOUS HALOGEN COMPOUND INTO LIQUID METAL.

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FR8106134 1981-03-23
FR8106134A FR2502181B1 (en) 1981-03-23 1981-03-23 PROCESS AND APPARATUS FOR THE PRECISE AND CONTINUOUS INJECTION OF A HALOGENATED DERIVATIVE IN A GASEOUS STATE IN A LIQUID METAL

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US4552667A (en) * 1984-06-25 1985-11-12 Shultz Clifford G Destruction of organic hazardous wastes
US4666696A (en) * 1985-03-29 1987-05-19 Detox International Corporation Destruction of nerve gases and other cholinesterase inhibitors by molten metal reduction
EP0436465A1 (en) * 1989-12-20 1991-07-10 Alusuisse-Lonza Services Ag Refining of molten metal
FR2669041A1 (en) * 1990-11-09 1992-05-15 Sfrm Process for the treatment of a molten metal and its transfer into a receiving cavity and system for making use of this process

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US4959101A (en) * 1987-06-29 1990-09-25 Aga Ab Process for degassing aluminum melts with sulfur hexafluoride
US5935295A (en) * 1997-10-16 1999-08-10 Megy; Joseph A. Molten aluminum treatment
WO2004033736A1 (en) 2002-10-07 2004-04-22 International Titanium Powder, Llc. System and method of producing metals and alloys
EA006616B1 (en) 2002-09-07 2006-02-24 Интернэшнл Тайтейнием Паудер, Ллк Process for separating titan from a titan slurry
AU2003278765A1 (en) * 2002-09-07 2004-04-08 International Titanium Powder, Llc. Method and apparatus for controlling the size of powder produced by the armstrong process
US20070017319A1 (en) 2005-07-21 2007-01-25 International Titanium Powder, Llc. Titanium alloy
WO2007044635A2 (en) 2005-10-06 2007-04-19 International Titanium Powder, Llc Titanium or titanium alloy with titanium boride dispersion
US7753989B2 (en) 2006-12-22 2010-07-13 Cristal Us, Inc. Direct passivation of metal powder
US9127333B2 (en) 2007-04-25 2015-09-08 Lance Jacobsen Liquid injection of VCL4 into superheated TiCL4 for the production of Ti-V alloy powder

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US4666696A (en) * 1985-03-29 1987-05-19 Detox International Corporation Destruction of nerve gases and other cholinesterase inhibitors by molten metal reduction
EP0436465A1 (en) * 1989-12-20 1991-07-10 Alusuisse-Lonza Services Ag Refining of molten metal
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DK127382A (en) 1982-09-24
ES8306803A1 (en) 1983-06-01
US4402741A (en) 1983-09-06
NO820940L (en) 1982-09-24
ATE20541T1 (en) 1986-07-15
KR830008767A (en) 1983-12-14
DE3271823D1 (en) 1986-07-31
ES510623A0 (en) 1983-06-01
CA1180164A (en) 1985-01-02
AU8176882A (en) 1982-09-30
FR2502181B1 (en) 1985-09-27
AU541804B2 (en) 1985-01-17
FR2502181A1 (en) 1982-09-24
JPS57164945A (en) 1982-10-09
GR76038B (en) 1984-08-03

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