EP0202174B1 - Process and apparatus for purifying lithium - Google Patents
Process and apparatus for purifying lithium Download PDFInfo
- Publication number
- EP0202174B1 EP0202174B1 EP86420106A EP86420106A EP0202174B1 EP 0202174 B1 EP0202174 B1 EP 0202174B1 EP 86420106 A EP86420106 A EP 86420106A EP 86420106 A EP86420106 A EP 86420106A EP 0202174 B1 EP0202174 B1 EP 0202174B1
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- EP
- European Patent Office
- Prior art keywords
- lithium
- temperature
- process according
- enclosure
- condensation
- Prior art date
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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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- 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
- C22B9/04—Refining by applying a vacuum
Definitions
- the present invention relates to a method and a device for purifying lithium, in particular sodium and potassium.
- the lithium used for this purpose must have a suitable purity, in particular it must contain very few alkali metals such as sodium and potassium because these elements significantly degrade the mechanical characteristics of aluminum alloys.
- the lithium obtained by chemical or electrochemical route generally contains sodium coming from the raw material and potassium in particular when it is manufactured electrolytically because this technique implements most often baths of molten salts containing chloride of potassium and that this compound dissociates partially during electrolysis, giving rise to a deposit of potassium simultaneously with lithium.
- lithium can be purified from potassium by distilling the hydride at around 700 ° C. or else simultaneously lowering the sodium and potassium content by distilling the lithium at around 400-450 ° C. under a very low pressure of the order from 1.10- 3 Pascal approximately.
- This process therefore consists in having melted the mass of lithium to be purified away from air in order to avoid its oxidation, in subjecting the bath thus formed to stirring so as to permanently renew the free surface which it presents. in the container where it was originally placed.
- This agitation can be obtained for any mechanical means such as agitator or electric such as electromagnetic coils supplied with alternating current, which induce in the bath of the electric forces which by interaction with the magnetic field which they create, develop forces of Laplace own to the commotion.
- the metal is maintained at a temperature between 400 and 700 ° C and reduced atmospheric pressure on the free surface of the bath to a value less than 10 Pascal, so as to cause evaporation.
- Maintaining the indicated temperature can be achieved by means of heating elements placed at the end of the bath so as to prevent their corrosion by lithium.
- this is obtained by any suitable pumping device, such as for example the combination of a vane pump and a diffusion pump.
- the chosen temperature range results from the fact that a higher temperature increases the lithium losses while a lower temperature reduces the rate of evaporation. In this range, a pressure below 10 Pascal must be maintained to have sufficient evaporation. But these conditions most favorable to the implementation of the method correspond to a temperature between 530 and 570 ° C and at a pressure between 1 and 1.10- 1.10- 3 Pascal.
- the process also includes a condensation phase which makes it possible to collect, in the liquid or solid state, the impurities which have evaporated.
- This condensation takes place at a temperature below 100 ° C and preferably below 50 ° C. It is indeed desirable to condense at the lowest possible temperature in order to be able to promote evaporation and to maintain a speed compatible with the desired productivity.
- the invention also includes a device for implementing the method.
- the condensation surface is at least equal to the evaporation surface in order to keep the process all its efficiency in purification.
- the enclosure having been purged of its air by introducing into (8) an argon current which can be evacuated by the valve, the impure lithium is introduced into the container by the supply means by following the level by means of the probe and heated by means of electrical resistances to the suitable temperature regulated by the thermocouple placed in (7).
- the enclosure is put under suitable pressure by switching on the pumping device while the lower part is cooled by sending a cold fluid into the jacket so as to maintain the temperature of the condensing surface at the desired value and controlled by the thermocouple placed in (19).
- the stirring means is then put into service.
- the impurities escape to the evaporation surface of the metal bath and the vapors condense on the condensation surface.
- the heat transfer fluid is brought to a temperature sufficient to melt the condensed impurities, preferably between 100 and 200 °.
Abstract
Description
La présente invention est relative à un procédé et à un dispositif de purification du lithium notamment en sodium et en potassium.The present invention relates to a method and a device for purifying lithium, in particular sodium and potassium.
On sait que le lithium est intéressant notamment dans l'industrie aéronautique où, allié à l'aluminium, il permet de confectionner des tôles et pièces massives, allégées, et d'améliorer certaines caractéristiques mécaniques des alliages classiques.We know that lithium is interesting in particular in the aeronautical industry where, combined with aluminum, it makes it possible to make sheets and massive, lightened parts, and to improve certain mechanical characteristics of conventional alloys.
Toutefois, le lithium utilisé à cette fin doit avoir une pureté convenable, en particulier il doit contenir très peu de métaux alcalins tels que le sodium et le potassium car ces éléments dégradent notablement les caractéristiques mécaniques des alliages d'aluminium.However, the lithium used for this purpose must have a suitable purity, in particular it must contain very few alkali metals such as sodium and potassium because these elements significantly degrade the mechanical characteristics of aluminum alloys.
Or, le lithium obtenu par voie chimique ou électrochimique contient généralement du sodium provenant de la matière première et du potassium notamment lorsqu'il est fabriqué électrolytique- ment parce que cette technique met en oeuvre le plus souvent des bains de sels fondus contenant du chlorure de potassium et que ce composé se dissocie partiellement lors de l'électrolyse en donnant lieu à un dépôt de potassium simultanément avec le lithium.However, the lithium obtained by chemical or electrochemical route generally contains sodium coming from the raw material and potassium in particular when it is manufactured electrolytically because this technique implements most often baths of molten salts containing chloride of potassium and that this compound dissociates partially during electrolysis, giving rise to a deposit of potassium simultaneously with lithium.
Il s'avère donc nécessaire de procéder à une purification du lithium en ces éléments avant d'entreprendre l'élaboration d'alliages avec l'aluminium.It therefore appears necessary to carry out a purification of the lithium in these elements before undertaking the development of alloys with aluminum.
Il est connu par le traité de Chimie Minérale de Pascal Tome II, 1er fascicule, édition 1966, p. 25 que l'on peut purifier le lithium en potassium en distillant l'hydrure vers 700°C ou encore abaisser simultanément la teneur en sodium et en potassium en distillant le lithium vers 400-450 °C sous une très faible pression de l'ordre de 1.10-3 Pascal environ.It is known by the treaty of Mineral Chemistry of Pascal Tome II, 1st fascicle, edition 1966, p. 25 that lithium can be purified from potassium by distilling the hydride at around 700 ° C. or else simultaneously lowering the sodium and potassium content by distilling the lithium at around 400-450 ° C. under a very low pressure of the order from 1.10- 3 Pascal approximately.
Mais ces procédés nécessitent la vaporisation complète du lithium d'où une consommation d'énergie calorifique relativement importante. De plus, le coefficient de séparation de ces métaux étant faible, la distillation doit être menée lentement si on veut obtenir la pureté convenable. Cela entraîne une faible productivité et n'empêche pas pour autant une perte importante de lithium à la fois sous forme polluée et par volatilisation.However, these processes require the complete vaporization of the lithium, hence a relatively high calorific energy consumption. In addition, the separation coefficient of these metals being low, the distillation must be carried out slowly if one wants to obtain the suitable purity. This results in low productivity and does not prevent a significant loss of lithium both in polluted form and by volatilization.
De plus, le ruissellement de lithium liquide sur les parois de la colonne de distillation est la cause d'une corrosion importante du matériel généralement réalisé en acier inoxydable qui peut engendrer des pollutions rédhibitoires du métal obtenu.In addition, the runoff of liquid lithium on the walls of the distillation column is the cause of significant corrosion of the material generally made of stainless steel which can cause unacceptable pollution of the metal obtained.
C'est pourquoi la demanderesse ayant constaté ces inconvénients a cherché et trouvé un procédé beaucoup plus rapide, moins polluant et plus économique que les précédents ainsi qu'un dispositif permettant la mise en oeuvre dudit procédé.This is why the Applicant, having observed these drawbacks, has sought and found a process that is much faster, less polluting and more economical than the previous ones, as well as a device allowing the implementation of said process.
L'invention a pour objet un procédé selon lequel:
- - on fond sous atmosphère inerte le lithium à purifier,
- - on agite le bain ainsi constitué tout en le portant à une température comprise entre 400 et 700°C et en le soumettant à une pression inférieure à 10 Pascal de manière à évaporer sélectivement les impuretés,
- - on condense les impuretés vaporisées à une température inférieure à 100°C.
- the lithium to be purified is melted under an inert atmosphere,
- the bath thus formed is stirred while bringing it to a temperature of between 400 and 700 ° C. and subjecting it to a pressure of less than 10 Pascal so as to selectively evaporate the impurities,
- - the vaporized impurities are condensed at a temperature below 100 ° C.
Ce procédé consiste donc après avoir fondu la masse de lithium à purifier à l'abri de l'air afin d'éviter son oxydation, à soumettre le bain ainsi formé à une agitation de façon à renouveler en permanence la surface libre qu'il présente dans le conteneur où il a été initialement placé. Cette agitation peut être obtenue pour tout moyen mécanique tel qu'agitateur ou électrique tel que bobines électromagnétiques alimentées en courant alternatif, lesquelles induisent dans le bain des forces électriques qui par interaction avec le champ magnétique qu'elles créent, développent des forces de Laplace propres à l'agitation. En même temps qu'on agite, on maintient le métal à une température comprise entre 400 et 700 °C et réduit la pression atmosphérique à la surface libre du bain à une valeur inférieure à 10 Pascal, de manière à y provoquer une évaporation.This process therefore consists in having melted the mass of lithium to be purified away from air in order to avoid its oxidation, in subjecting the bath thus formed to stirring so as to permanently renew the free surface which it presents. in the container where it was originally placed. This agitation can be obtained for any mechanical means such as agitator or electric such as electromagnetic coils supplied with alternating current, which induce in the bath of the electric forces which by interaction with the magnetic field which they create, develop forces of Laplace own to the commotion. While stirring, the metal is maintained at a temperature between 400 and 700 ° C and reduced atmospheric pressure on the free surface of the bath to a value less than 10 Pascal, so as to cause evaporation.
Le maintien à la température indiquée peut être réalisé au moyen d'éléments chauffants placés à l'extrémité du bain de manière à éviter leur corrosion par le lithium. Quant à la pression réduite, elle est obtenue par tout dispositif de pompage convenable, tel que par exemple l'association d'une pompe à palettes et d'une pompe à diffusion.Maintaining the indicated temperature can be achieved by means of heating elements placed at the end of the bath so as to prevent their corrosion by lithium. As for the reduced pressure, this is obtained by any suitable pumping device, such as for example the combination of a vane pump and a diffusion pump.
La fourchette de température retenue résulte du fait qu'une température plus haute augmente les pertes en lithium tandis qu'une température plus basse réduit la vitesse d'évaporation. Dans cette fourchette, une pression inférieure à 10 Pascal doit être maintenue pour avoir une évaporation suffisante. Mais ces conditions les plus favorables à la mise en oeuvre du procédé correspondent à une température comprise entre 530 et 570 °C et à une pression comprise entre 1.10-1 et 1.10-3 Pascal.The chosen temperature range results from the fact that a higher temperature increases the lithium losses while a lower temperature reduces the rate of evaporation. In this range, a pressure below 10 Pascal must be maintained to have sufficient evaporation. But these conditions most favorable to the implementation of the method correspond to a temperature between 530 and 570 ° C and at a pressure between 1 and 1.10- 1.10- 3 Pascal.
L'évaporation réalisée dans ces conditions s'avère être alors très sélective, c'est-à-dire qu'elle affecte presque exclusivement les impuretés: sodium et potassium sans entraîner d'évaporation sensible de lithium et cela, avec des vitesses relativement grandes permettant ainsi d'obtenir une productivité convenable. En raison de la nature des moyens de l'invention, le problème de la corrosion et de la pollution qui lui est consécutive est supprimé.The evaporation carried out under these conditions turns out to be very selective, that is to say that it almost exclusively affects the impurities: sodium and potassium without causing appreciable evaporation of lithium and this, with relatively high speeds. thus allowing to obtain a suitable productivity. Due to the nature of the means of the invention, the problem of corrosion and of the pollution which follows from it is eliminated.
Le procédé comprend également une phase de condensation qui permet de recueillir à l'état liquide ou solide, les impuretés qui se sont évaporées. Cette condensation s'effectue à une température inférieure à 100°C et de préférence inférieure à 50°C. Il est en effet souhaitable de condenser à la température la plus basse possible afin de pouvoir favoriser l'évaporation et de maintenir une vitesse compatible avec la productivité recherchée.The process also includes a condensation phase which makes it possible to collect, in the liquid or solid state, the impurities which have evaporated. This condensation takes place at a temperature below 100 ° C and preferably below 50 ° C. It is indeed desirable to condense at the lowest possible temperature in order to be able to promote evaporation and to maintain a speed compatible with the desired productivity.
L'envention comprend également un dispositif pour la mise en application du procédé.The invention also includes a device for implementing the method.
Ce dispositif est caractérisé en ce qu'il est constitué par une enceinte métallique étanche à l'air ambiant formée de:
- - une partie haute, équipée de moyens de chauffage, d'agitation, d'alimentation et de prélèvement du lithium, de mesure de niveau et de température, et à l'intérieur de laquelle est placé un conteneur où le lithium présente une surface d'évaporation vers l'enceinte;
- - une partie basse équipée de moyens de transfert calorifique, d'une vanne de vidange et d'une tuyauterie reliée à un dispositif de pompage et à l'intérieur de laquelle est placée une surface de révolution destinée à la condensation, fixée de façon étanche sur toute sa périphérie extérieure et au moins sur une fraction de sa hauteur à la paroi intérieure de l'enceinte, l'intérieur de ladite surface mettant en communication la partie haute de l'enceinte avec la tuyauterie.
- - an upper part, equipped with means for heating, stirring, supplying and withdrawing lithium, level and temperature measurement, and inside which is placed a container where the lithium has a surface d evaporation to the enclosure;
- - a lower part equipped with heat transfer means, a drain valve and a pipe connected to a pumping device and inside which is placed a surface of revolution intended for condensation, fixed in a sealed manner over its entire outer periphery and at least over a fraction of its height to the inner wall of the enclosure, the interior of said surface communicating the upper part of the enclosure with the piping.
Dans ce dispositif, la surface de condensation est au moins égale à la surface d'évaporation afin de garder au procédé toute son efficacité dans la purification.In this device, the condensation surface is at least equal to the evaporation surface in order to keep the process all its efficiency in purification.
La description d'un tel dispositif est facilitée en s'aidant de la figure jointe qui représente en coupe axiale verticale un dispositif particulier.The description of such a device is facilitated by using the attached figure which represents a particular device in vertical axial section.
On y voit une enceinte cylindro-conique en acier, étanche à l'air ambiant, formée:
- -d'une partie haute (1) cylindrique, chauffée au moyen de résistances électriques (2) équipée de moyens d'agitation ici constitués par une bobine (3) circulaire dans laquelle circule un courant électrique alternatif, de moyens d'alimentation (4) et de prélèvement (5) du lithium, d'une sonde (6) de mesure de niveau du lithium, d'un tube borgne (7) dans lequel est placé un thermocouple, d'un piquage (8) d'introduction de gaz neutre; à l'intérieur de cette partie est placé un conteneur (9) en acier NSMC revêtu intérieurement de fer pur, suspendu au dôme de l'enceinte par des supports (10) et refermant le bain (11) de lithium qui présente une surface d'évaporation (12);
- - d'une partie basse (13) conique, présentant une double enveloppe (14) à l'intérieur de laquelle circule un fluide caloporteur, équipée à sa partie inférieure d'une vanne (15) de vidange des impuretés et sur sa partie latérale d'une tuyauterie (16) reliée à un dispositif de pompage non représenté; à l'intérieur de cette partie est placée une surface (17) de révolution destinée à la condensation, fixée de façon étanche sur toute sa périphérie extérieure suivant la couronne (18) à la paroi intérieure de l'enceinte et mettant en relation la partie haute de l'enceinte avec la tuyauterie. Sur cette surface est fixée une gaine (19) permettant de loger un thermocouple destiné à contrôler la température de condensation.
- -a cylindrical upper part (1), heated by means of electrical resistors (2) equipped with stirring means here constituted by a circular coil (3) in which an alternating electric current flows, by supply means (4 ) and lithium sampling (5), a lithium level probe (6), a blind tube (7) in which a thermocouple is placed, a nozzle (8) for introducing neutral gas; inside this part is placed a container (9) in NSMC steel coated internally with pure iron, suspended from the dome of the enclosure by supports (10) and closing the bath (11) of lithium which has a surface d 'evaporation (12);
- - a conical lower part (13), having a double envelope (14) inside which circulates a heat transfer fluid, equipped at its lower part with a valve (15) for emptying of impurities and on its lateral part a pipe (16) connected to a pumping device not shown; inside this part is placed a surface (17) of revolution intended for condensation, fixed in leaktight fashion over its entire outer periphery along the crown (18) to the inner wall of the enclosure and relating the part high of the enclosure with piping. On this surface is fixed a sheath (19) for housing a thermocouple intended to control the condensation temperature.
Le fonctionnement d'un tel dispositif est le suivant: l'enceinte ayant été purgée de son air par introduction en (8) d'un courant d'argon que l'on peut évacuer par la vanne, le lithium impur est introduit dans le conteneur par le moyen d'alimentation en suivant le niveau au moyen de la sonde et chauffé au moyen de résistances électriques à la température convenable régulée par le thermocouple placé en (7). L'enceinte est mise sous pression convenable par mise en route du dispositif de pompage tandis que la partie inférieure est refroidie par envoi d'un fluide froid dans la double enveloppe de manière à maintenir la température de la surface de condensation à la valeur désirée et contrôlée par le thermocouple placé en (19).The operation of such a device is as follows: the enclosure having been purged of its air by introducing into (8) an argon current which can be evacuated by the valve, the impure lithium is introduced into the container by the supply means by following the level by means of the probe and heated by means of electrical resistances to the suitable temperature regulated by the thermocouple placed in (7). The enclosure is put under suitable pressure by switching on the pumping device while the lower part is cooled by sending a cold fluid into the jacket so as to maintain the temperature of the condensing surface at the desired value and controlled by the thermocouple placed in (19).
Le moyen d'agitation est alors mis en service. Les impuretés s'échappent à la surface d'évaporation du bain métallique et les vapeurs viennent se condenser sur la surface de condensation.The stirring means is then put into service. The impurities escape to the evaporation surface of the metal bath and the vapors condense on the condensation surface.
Après une durée d'agitation fonction de la quantité de lithium, de sa composition et du degré de pureté souhaité, le moyen d'agitation et le groupe de pompage sont arrêtés; le lithium purifié est prélevé et les impuretés vidangées par l'intermédiaire de la vanne de fond (15).After a stirring period depending on the amount of lithium, its composition and the desired degree of purity, the stirring means and the pumping unit are stopped; the purified lithium is removed and the impurities discharged via the bottom valve (15).
Pour permettre cette vidange, le fluide caloporteur est porté à une température suffisante pour fondre les impuretés condensées, de préférence entre 100 et 200°.To allow this emptying, the heat transfer fluid is brought to a temperature sufficient to melt the condensed impurities, preferably between 100 and 200 °.
L'invention peut être illustrée à l'aide de l'exemple d'application suivant:
- Une charge de 10 kg de lithium contenant en poids 200 ppm de sodium et 100 ppm de potassium à été traité à 550°C sous 1.10-2 Pascal pendant 6 heures dans un dispositif où la surface de condensation était égale à 2 fois la surface d'évaporation. La température de la surface de condensation était de 100°C. On a récupéré 9,95 kg de lithium qui renfermait 5 ppm de sodium et 2 ppm de potassium.
- Ces chiffres montrent l'efficacité du procédé selon l'invention qui trouve son application notamment dans la purification du lithium destiné notamment à l'élaboration d'alliages d'aluminium pour les besoins de l'aéronautique.
- A load of 10 kg by weight lithium containing 200 ppm sodium and 100 ppm potassium was treated at 550 ° C under 1.10- 2 Pa for 6 hours in a device where the condensing surface was equal to 2 times the surface 'evaporation. The temperature of the condensing surface was 100 ° C. 9.95 kg of lithium were recovered, which contained 5 ppm of sodium and 2 ppm of potassium.
- These figures show the effectiveness of the process according to the invention which finds its application in particular in the purification of lithium intended in particular for the development of aluminum alloys for the needs of aeronautics.
Claims (8)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AT86420106T ATE35293T1 (en) | 1985-04-24 | 1986-04-22 | METHOD AND DEVICE FOR LITHIUM REFINING. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR8506606 | 1985-04-24 | ||
| FR8506606A FR2581080B1 (en) | 1985-04-24 | 1985-04-24 | LITHIUM PURIFICATION PROCESS AND DEVICE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP0202174A1 EP0202174A1 (en) | 1986-11-20 |
| EP0202174B1 true EP0202174B1 (en) | 1988-06-22 |
Family
ID=9318850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP86420106A Expired EP0202174B1 (en) | 1985-04-24 | 1986-04-22 | Process and apparatus for purifying lithium |
Country Status (12)
| Country | Link |
|---|---|
| US (2) | US4738716A (en) |
| EP (1) | EP0202174B1 (en) |
| JP (2) | JPS61253331A (en) |
| CN (1) | CN1004081B (en) |
| AT (1) | ATE35293T1 (en) |
| CA (1) | CA1272033A (en) |
| DD (1) | DD244766A5 (en) |
| DE (1) | DE3660338D1 (en) |
| ES (1) | ES8704550A1 (en) |
| FR (1) | FR2581080B1 (en) |
| IL (1) | IL78580A (en) |
| IN (1) | IN162925B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4781756A (en) * | 1987-07-02 | 1988-11-01 | Lithium Corporation Of America | Removal of lithium nitride from lithium metal |
| DE8811839U1 (en) * | 1988-09-17 | 1989-02-02 | Degussa Ag, 6000 Frankfurt, De | |
| CN1059709C (en) * | 1997-11-05 | 2000-12-20 | 北京市吉利源***工程公司 | Method and equipment for vacuum distillation puritying metallic lithium |
| US6048507A (en) * | 1997-12-09 | 2000-04-11 | Limtech | Process for the purification of lithium carbonate |
| EP1335993B1 (en) * | 2000-10-27 | 2004-11-17 | McGILL UNIVERSITY | Recovery of purified volatile metal such as lithium from mixed metal vapours |
| CN100487143C (en) * | 2003-11-14 | 2009-05-13 | 昆明永年锂业有限公司 | Process for preparing high purity lithium |
| CN100339498C (en) * | 2005-06-16 | 2007-09-26 | 王洪 | High sodium metal lithium and its manufacturing method |
| CN100432248C (en) * | 2006-06-27 | 2008-11-12 | 戴日桃 | Very-pure metal lithium refining and purification process |
| CN101892394B (en) * | 2009-12-18 | 2013-07-24 | 中南大学 | Method and device for extracting lithium from lithium mica |
| US8679224B2 (en) | 2011-08-31 | 2014-03-25 | Babcock & Wilcox Technical Services Y-12, Llc | Hydrogen, lithium, and lithium hydride production |
| CN104388688B (en) * | 2014-11-17 | 2016-07-06 | 东北大学 | A kind of device and method of vacuum metal thermal reduction refining lithium |
| CN108107092B (en) * | 2017-11-17 | 2019-09-27 | 清华大学 | A kind of infiltration preparation method of the lithium ion battery with reference electrode |
| US11761057B1 (en) | 2022-03-28 | 2023-09-19 | Lyten, Inc. | Method for refining one or more critical minerals |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2879157A (en) * | 1955-10-04 | 1959-03-24 | Mine Safety Appliances Co | Purification of alkali metals by heat transfer |
| JPS5224104A (en) * | 1975-07-23 | 1977-02-23 | Vladimir Semenobuitsuchi Chier | Apparatus for continuous vacuum refining of metals |
| JPS52133010A (en) * | 1976-04-30 | 1977-11-08 | Japan Atom Energy Res Inst | Purifying apparatus for liquid metallic lithium |
| CH659000A5 (en) * | 1981-11-07 | 1986-12-31 | Leybold Heraeus Gmbh & Co Kg | DISTILLATION AND SUBLIMATION DEVICE WITH A CONDENSER. |
| JPS61133331A (en) * | 1984-11-30 | 1986-06-20 | Toyota Motor Corp | Method and device for distilling metal |
| FR2574091B1 (en) * | 1984-12-04 | 1988-12-23 | Novatome | PROCESS AND DEVICE FOR PRE-TREATING LIQUID SODIUM CONTAINING DISSOLVED IMPURITIES |
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1985
- 1985-04-24 FR FR8506606A patent/FR2581080B1/en not_active Expired
-
1986
- 1986-04-15 CN CN86102633.0A patent/CN1004081B/en not_active Expired
- 1986-04-16 US US06/852,552 patent/US4738716A/en not_active Expired - Lifetime
- 1986-04-21 IN IN310/CAL/86A patent/IN162925B/en unknown
- 1986-04-22 AT AT86420106T patent/ATE35293T1/en not_active IP Right Cessation
- 1986-04-22 EP EP86420106A patent/EP0202174B1/en not_active Expired
- 1986-04-22 IL IL78580A patent/IL78580A/en not_active IP Right Cessation
- 1986-04-22 DE DE8686420106T patent/DE3660338D1/en not_active Expired
- 1986-04-22 CA CA000507302A patent/CA1272033A/en not_active Expired - Fee Related
- 1986-04-22 JP JP61093180A patent/JPS61253331A/en active Granted
- 1986-04-23 ES ES554264A patent/ES8704550A1/en not_active Expired
- 1986-04-23 DD DD86289540A patent/DD244766A5/en not_active IP Right Cessation
-
1987
- 1987-12-16 US US07/133,882 patent/US4842254A/en not_active Expired - Lifetime
-
1988
- 1988-03-09 JP JP63055953A patent/JP2615124B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US4842254A (en) | 1989-06-27 |
| FR2581080A1 (en) | 1986-10-31 |
| CA1272033A (en) | 1990-07-31 |
| JPH0368937B2 (en) | 1991-10-30 |
| DE3660338D1 (en) | 1988-07-28 |
| ATE35293T1 (en) | 1988-07-15 |
| CN86102633A (en) | 1986-12-03 |
| JPS6479330A (en) | 1989-03-24 |
| CN1004081B (en) | 1989-05-03 |
| IL78580A0 (en) | 1986-08-31 |
| IN162925B (en) | 1988-07-23 |
| FR2581080B1 (en) | 1987-06-19 |
| US4738716A (en) | 1988-04-19 |
| JP2615124B2 (en) | 1997-05-28 |
| DD244766A5 (en) | 1987-04-15 |
| IL78580A (en) | 1989-01-31 |
| JPS61253331A (en) | 1986-11-11 |
| ES8704550A1 (en) | 1987-04-01 |
| EP0202174A1 (en) | 1986-11-20 |
| ES554264A0 (en) | 1987-04-01 |
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