EP1258536B1 - Purification process for Sodium - Google Patents

Purification process for Sodium Download PDF

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Publication number
EP1258536B1
EP1258536B1 EP02356088A EP02356088A EP1258536B1 EP 1258536 B1 EP1258536 B1 EP 1258536B1 EP 02356088 A EP02356088 A EP 02356088A EP 02356088 A EP02356088 A EP 02356088A EP 1258536 B1 EP1258536 B1 EP 1258536B1
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EP
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Prior art keywords
sodium
gas
inert gas
water
calcium
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EP02356088A
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German (de)
French (fr)
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EP1258536A1 (en
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Pierre Flacher
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MSSA
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MSSA
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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
    • 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 invention relates to a process for purifying industrial grade sodium. to significantly reduce its calcium content.
  • Sodium produced industrially by electrolysis of sodium chloride melted generally has a calcium content of 400 to 500 ppm. This content is greater than the limit of solubility of calcium in molten sodium at usual temperatures of use in the industry, so that one risks a deposit of calcium in installations transporting liquid sodium. In addition, for some applications, such as in the nuclear field, this purity is insufficient and, for this reason, different purification methods have been proposed and implemented for several decades.
  • Patent FR1484647 filed in 1965 by the French Atomic Energy Commission, has describes the use of sodium peroxide to remove calcium. The process is to mix sodium and peroxide in a reactor at a temperature between 200 and 300 ° C with vigorous stirring, and to remove the solid lime particles by filtration. We can thus obtain a sodium at less than 10 ppm calcium.
  • Patent FR 1214176 to du Pont de Nemours published in 1960, describes a method of sodium purification consisting of mixing molten sodium at a temperature below 300 ° C with an inert gas, in particular nitrogen, containing from 0.1 to 2%, and preferably 0.1 to 0.5% oxygen, the gas being recycled after passage.
  • an inert gas in particular nitrogen, containing from 0.1 to 2%, and preferably 0.1 to 0.5% oxygen, the gas being recycled after passage.
  • the patent indicates that adding water vapor to the inert gas instead of oxygen is ineffective because it does not help to make the insoluble calcium to separate it by filtration, decantation or centrifugation.
  • the object of the invention is to provide a process for the purification of sodium by oxidation. simpler, less expensive and at least as effective as calcium prior art.
  • the object of the invention is a process for the purification of technical sodium consisting bringing the liquid sodium into contact at a temperature equal to or greater than 150 ° C, as described in claim 1.
  • the invention is based on the finding made by the applicant that, in certain conditions of implementation, and contrary to the teaching of the FR patent 1214176, the use of water vapor as an oxidant for calcium could lead to simple and efficient sodium purification.
  • the process is based on the oxidation reaction: Ca + H 2 O ⁇ CaO + H 2 .
  • the quantity of water required for a given quantity of sodium is the stoichiometric quantity corresponding to the calcium that we want to eliminate, that is to say the difference between the starting calcium content and that which we aim at. arrival.
  • the process being continuous, this supposes that the ratio K between the water flow rate and the sodium flow rate is kept almost constant. The operation is done in a static mixer favoring a good exchange between the liquid sodium and the gases.
  • the inert gas which is preferably nitrogen, but can also be argon, has the function on the one hand of diluting the water vapor and bringing it into contact with sodium, and on the other hand of 'ensure the evacuation of the hydrogen formed by the reaction.
  • the amount of nitrogen required per gram of water is preferably between 30 and 40 dm 3 / g. This quantity is clearly lower than that mentioned in patent FR 1214176, which recommends a ratio of the volume of dispersion gas to the volume of sodium of between 20 and 200, while the quantity mentioned above leads, for an almost complete purification. in calcium, at a ratio of the order of 6. This makes it possible to avoid recycling of the gas, which greatly simplifies the installation.
  • the temperature of the liquid sodium in the mixer must be equal to or higher than 150 ° C to avoid any risk of fouling of the mixer. It is best to avoid excessively high temperatures, for example above 250 ° C, both for safety reasons and to avoid corrosion of the installation.
  • the purified sodium is first separated from the gases through a degasser, then lime by filtration.
  • the single figure is a block diagram of the method according to the invention.
  • the example relates to a pilot installation using the method according to the invention.
  • the technical sodium is conveyed to the static mixer (1) using a pump (2)
  • the water is sent, using a pump (3) to an evaporator (4) to a temperature regulated at 130 ° C.
  • With the pump (3) is associated a regulation in function of the sodium flow measured by a flow meter, so as to keep constant the report K.
  • the dry nitrogen is sent, through a flow meter (5) to the evaporator (4).
  • the wet nitrogen is then directed to the static mixer (1) in a pipe traced and insulated to avoid condensation of water.
  • a non-return valve on this same pipe prevents the passage of sodium to the evaporator (4).
  • Purified sodium containing precipitated lime and nitrogen with hydrogen from reaction passes through a degasser (6), where it releases nitrogen and hydrogen, then to through filters (7) to separate the lime.
  • the installation is started with dry nitrogen, no water being introduced until the normal sodium flow is reached.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Removal Of Specific Substances (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

Purification of sodium to reduce its calcium content involves contacting, at a temperature equal to or greater than 150 degrees C inside a static mixer, with a current of gas, inert with respect to sodium, charged with water vapor in a stoichiometric quantity necessary for oxidizing the calcium to lower its content to a desired level, and separating the purified sodium from the inert gas and the hydrogen and lime products from the reaction. The inert gas used may be nitrogen or argon.

Description

Domaine techniqueTechnical area

L'invention concerne un procédé de purification du sodium de qualité industrielle pour réduire notablement sa teneur en calcium.The invention relates to a process for purifying industrial grade sodium. to significantly reduce its calcium content.

Etat de la techniqueState of the art

Le sodium produit de manière industrielle par électrolyse du chlorure de sodium fondu présente généralement une teneur en calcium de 400 à 500 ppm. Cette teneur est supérieure à la limite de solubilité du calcium dans le sodium fondu aux températures usuelles d'utilisation dans l'industrie, de sorte qu'on risque un dépôt de calcium dans les installations véhiculant le sodium liquide. De plus, pour certaines applications, comme par exemple dans le domaine nucléaire, cette pureté est insuffisante et, pour cette raison, différents procédés de purification ont été proposés et mis en oeuvre depuis plusieurs décennies.Sodium produced industrially by electrolysis of sodium chloride melted generally has a calcium content of 400 to 500 ppm. This content is greater than the limit of solubility of calcium in molten sodium at usual temperatures of use in the industry, so that one risks a deposit of calcium in installations transporting liquid sodium. In addition, for some applications, such as in the nuclear field, this purity is insufficient and, for this reason, different purification methods have been proposed and implemented for several decades.

Le brevet FR1484647, déposé en 1965 par le Commissariat à l'Energie Atomique, a décrit l'utilisation du peroxyde de sodium pour éliminer le calcium. Le procédé consiste à mélanger le sodium et le peroxyde dans un réacteur à une température comprise entre 200 et 300°C avec une agitation vigoureuse, et à éliminer les particules solides de chaux par filtration. On peut ainsi obtenir un sodium à moins de 10 ppm de calcium.Patent FR1484647, filed in 1965 by the French Atomic Energy Commission, has describes the use of sodium peroxide to remove calcium. The process is to mix sodium and peroxide in a reactor at a temperature between 200 and 300 ° C with vigorous stirring, and to remove the solid lime particles by filtration. We can thus obtain a sodium at less than 10 ppm calcium.

Le brevet FR 2251627 de la demanderesse, déposé en 1973, a perfectionné le procédé précédent pour remédier à certains inconvénients comme le caractère discontinu du procédé, les dépôts solides sur les parois du réacteur et la consommation très élevée de peroxyde.The applicant's patent FR 2251627, filed in 1973, perfected the process precedent to remedy certain disadvantages such as the discontinuous nature of the process, solid deposits on the reactor walls and very high consumption of peroxide.

Un tel procédé n'est cependant pas économiquement adapté à la purification de sodium pour des applications plus courantes, pour lesquelles on souhaite une réduction plus ou moins importante de la teneur en calcium, sans être lié par les normes rigoureuses de l'industrie nucléaire.However, such a process is not economically suitable for the purification of sodium for more common applications, for which a more or less significant reduction in calcium content, without being bound by stringent standards in the nuclear industry.

Le brevet FR 1214176 de du Pont de Nemours, publié en 1960, décrit un procédé de purification du sodium consistant à mélanger le sodium en fusion à une température inférieure à 300°C avec un gaz inerte, notamment l'azote, contenant de 0,1 à 2%, et de préférence de 0,1 à 0,5% d'oxygène, le gaz étant recyclé après passage. Le brevet indique que l'ajout de vapeur d'eau dans le gaz inerte à la place de l'oxygène est inefficace, car il ne contribue pas à rendre le calcium insoluble pour le séparer par filtration, décantation ou centrifugation.Patent FR 1214176 to du Pont de Nemours, published in 1960, describes a method of sodium purification consisting of mixing molten sodium at a temperature below 300 ° C with an inert gas, in particular nitrogen, containing from 0.1 to 2%, and preferably 0.1 to 0.5% oxygen, the gas being recycled after passage. The patent indicates that adding water vapor to the inert gas instead of oxygen is ineffective because it does not help to make the insoluble calcium to separate it by filtration, decantation or centrifugation.

Objet de l'inventionSubject of the invention

L'invention a pour but d'offrir un procédé de purification du sodium par oxydation du calcium plus simple, moins coûteux et au moins aussi efficace que les procédés de l'art antérieur.The object of the invention is to provide a process for the purification of sodium by oxidation. simpler, less expensive and at least as effective as calcium prior art.

L'objet de l'invention est un procédé de purification du sodium technique consistant à mettre en contact le sodium liquide à une température égale ou supérieure à 150°C, tel que décrit dans la revendication 1.The object of the invention is a process for the purification of technical sodium consisting bringing the liquid sodium into contact at a temperature equal to or greater than 150 ° C, as described in claim 1.

Description de l'inventionDescription of the invention

L'invention repose sur la constatation faite par la demanderesse que, dans certaines conditions de mise en oeuvre, et contrairement à l'enseignement du brevet FR 1214176, l'utilisation de vapeur d'eau comme oxydant du calcium pouvait conduire à une purification simple et efficace du sodium.The invention is based on the finding made by the applicant that, in certain conditions of implementation, and contrary to the teaching of the FR patent 1214176, the use of water vapor as an oxidant for calcium could lead to simple and efficient sodium purification.

Le procédé est basé sur la réaction d'oxydation : Ca + H2O → CaO + H2. En fait, il est probable que la réaction se passe en deux temps par l'intermédiaire de l'oxyde de sodium, soit : Na + H2O → NaO + H2 et NaO + Ca → Na + CaO. La quantité d'eau nécessaire pour une quantité donnée de sodium est la quantité stoechiométrique correspondant au calcium qu'on veut éliminer, c'est-à-dire la différence entre la teneur de calcium de départ et celle qu'on vise à l'arrivée. Le procédé étant continu, cela suppose de maintenir à peu près constant le rapport K entre le débit d'eau et le débit de sodium. L'opération se fait dans un mélangeur statique favorisant un bon échange entre le sodium liquide et les gaz. Le gaz inerte, qui est de préférence l'azote, mais peut être également l'argon, a pour fonction d'une part de diluer la vapeur d'eau et de l'amener au contact du sodium, et d'autre part d'assurer l'évacuation de l'hydrogène formé par la réaction. La quantité d'azote nécessaire par gramme d'eau est comprise de préférence entre 30 et 40 dm3/g. Cette quantité est nettement plus faible que celle mentionnée dans le brevet FR 1214176, qui préconise un rapport du volume de gaz de dispersion au volume de sodium compris entre 20 et 200, alors que la quantité mentionnée plus haut conduit, pour une purification quasi-complète en calcium, à un rapport de l'ordre de 6. Ceci permet d'éviter le recyclage du gaz, ce qui simplifie fortement l'installation.The process is based on the oxidation reaction: Ca + H 2 O → CaO + H 2 . In fact, it is likely that the reaction takes place in two stages via sodium oxide, namely: Na + H 2 O → NaO + H 2 and NaO + Ca → Na + CaO. The quantity of water required for a given quantity of sodium is the stoichiometric quantity corresponding to the calcium that we want to eliminate, that is to say the difference between the starting calcium content and that which we aim at. arrival. The process being continuous, this supposes that the ratio K between the water flow rate and the sodium flow rate is kept almost constant. The operation is done in a static mixer favoring a good exchange between the liquid sodium and the gases. The inert gas, which is preferably nitrogen, but can also be argon, has the function on the one hand of diluting the water vapor and bringing it into contact with sodium, and on the other hand of 'ensure the evacuation of the hydrogen formed by the reaction. The amount of nitrogen required per gram of water is preferably between 30 and 40 dm 3 / g. This quantity is clearly lower than that mentioned in patent FR 1214176, which recommends a ratio of the volume of dispersion gas to the volume of sodium of between 20 and 200, while the quantity mentioned above leads, for an almost complete purification. in calcium, at a ratio of the order of 6. This makes it possible to avoid recycling of the gas, which greatly simplifies the installation.

La température du sodium liquide dans le mélangeur doit être égale ou supérieure à 150°C pour éviter tout risque d'encrassement du mélangeur. Il est préférable d'éviter des températures trop élevées, par exemple supérieures à 250°C, à la fois pour des raisons de sécurité et pour éviter la corrosion de l'installation.The temperature of the liquid sodium in the mixer must be equal to or higher than 150 ° C to avoid any risk of fouling of the mixer. It is best to avoid excessively high temperatures, for example above 250 ° C, both for safety reasons and to avoid corrosion of the installation.

A la sortie du mélangeur, on sépare le sodium épuré d'abord des gaz à travers un dégazeur, puis de la chaux par filtration.At the outlet of the mixer, the purified sodium is first separated from the gases through a degasser, then lime by filtration.

Description des figuresDescription of the figures

La figure unique est un schéma de principe du procédé selon l'invention.The single figure is a block diagram of the method according to the invention.

Exemple de réalisationExample of realization

L'exemple concerne une installation pilote utilisant le procédé selon l'invention. Le sodium technique est véhiculé vers le mélangeur statique (1) à l'aide d'une pompe (2) L'eau est envoyée, à l'aide d'une pompe (3) vers un évaporateur (4) à une température régulée à 130°C. A la pompe (3) est associée une régulation en fonction du débit de sodium mesuré par un débitmètre, de manière à maintenir constant le rapport K. L'azote sec est envoyé, à travers un débitmètre (5) vers l'évaporateur (4).The example relates to a pilot installation using the method according to the invention. The technical sodium is conveyed to the static mixer (1) using a pump (2) The water is sent, using a pump (3) to an evaporator (4) to a temperature regulated at 130 ° C. With the pump (3) is associated a regulation in function of the sodium flow measured by a flow meter, so as to keep constant the report K. The dry nitrogen is sent, through a flow meter (5) to the evaporator (4).

L'azote humide est dirigé ensuite vers le mélangeur statique (1) dans une conduite tracée et calorifugée pour éviter la condensation de l'eau. De plus, un clapet anti-retour sur cette même conduite empêche le passage du sodium vers l'évaporateur (4). Le sodium épuré contenant la chaux précipitée et l'azote avec l'hydrogène issu de la réaction passe à travers un dégazeur (6), où il libère l'azote et l'hydrogène, puis à travers des filtres (7) pour séparer la chaux.The wet nitrogen is then directed to the static mixer (1) in a pipe traced and insulated to avoid condensation of water. In addition, a non-return valve on this same pipe prevents the passage of sodium to the evaporator (4). Purified sodium containing precipitated lime and nitrogen with hydrogen from reaction passes through a degasser (6), where it releases nitrogen and hydrogen, then to through filters (7) to separate the lime.

Le démarrage de l'installation se fait avec de l'azote sec, l'eau n'étant introduite qu'une fois le débit normal de sodium atteint. Pour arrêter l'installation, on arrête d'abord la pompe à eau (3), puis la pompe à sodium (2) et enfin le débit d'azote.The installation is started with dry nitrogen, no water being introduced until the normal sodium flow is reached. To stop the installation, we stop first the water pump (3), then the sodium pump (2) and finally the nitrogen flow.

En marche normale, on a un débit de sodium de 700kg/h, un débit d'eau de 122 g/h et un débit d'azote de 4000 l/h. La température dans le mélangeur est de 150°C. La teneur en calcium du sodium de départ est de 410 ppm et celle du sodium purifié de 27 ppm.In normal operation, there is a sodium flow of 700kg / h, a water flow of 122 g / h and a nitrogen flow of 4000 l / h. The temperature in the mixer is 150 ° C. The calcium content of the starting sodium is 410 ppm and that of the purified sodium of 27 ppm.

Claims (5)

  1. Continuous purification process for technical sodium to reduce its calcium content consisting in putting liquid sodium into contact with a current of gas inert to sodium containing water vapour at a temperature equal to or greater than 150°C, and then separating purified sodium from the inert gas, hydrogen and lime produced by the reaction, characterised in that water is added to the inert gas at a flow regulated as a function of the sodium flow so as to keep the ratio between the water flow and the sodium flow constant and so as to obtain the stoichiometric quantity of water necessary to oxidise the calcium.
  2. Process according to claim 1, in which the inert gas is nitrogen or argon.
  3. Process according to claim 2 in which the inert gas is nitrogen and the quantity is between 30 and 40 dm3 per gram of water contained in the gas.
  4. Process according to one of claims 1 to 3, in which sodium and gas are brought into contact in a static mixer.
  5. Process according to one of claims 1 to 4, in which sodium is filtered to separate the lime.
EP02356088A 2001-05-16 2002-05-13 Purification process for Sodium Expired - Lifetime EP1258536B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0106458A FR2824845B1 (en) 2001-05-16 2001-05-16 SODIUM PURIFICATION PROCESS
FR0106458 2001-05-16

Publications (2)

Publication Number Publication Date
EP1258536A1 EP1258536A1 (en) 2002-11-20
EP1258536B1 true EP1258536B1 (en) 2004-07-07

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EP02356088A Expired - Lifetime EP1258536B1 (en) 2001-05-16 2002-05-13 Purification process for Sodium

Country Status (7)

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US (1) US6773483B2 (en)
EP (1) EP1258536B1 (en)
JP (1) JP4180836B2 (en)
CN (1) CN1239722C (en)
AT (1) ATE270716T1 (en)
DE (1) DE60200705T2 (en)
FR (1) FR2824845B1 (en)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2054316A (en) * 1933-08-29 1936-09-15 Du Pont Separation of metals
US2863757A (en) * 1956-12-23 1958-12-09 Du Pont Process for the removal of calcium from sodium
FR1214176A (en) * 1958-09-02 1960-04-07 Du Pont Calcium-sodium separation process
FR2251627B1 (en) * 1973-11-16 1976-11-19 Metaux Speciaux Sa

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CN1389585A (en) 2003-01-08
ATE270716T1 (en) 2004-07-15
DE60200705T2 (en) 2005-07-28
US20020170390A1 (en) 2002-11-21
US6773483B2 (en) 2004-08-10
CN1239722C (en) 2006-02-01
EP1258536A1 (en) 2002-11-20
FR2824845B1 (en) 2003-06-27
DE60200705D1 (en) 2004-08-12
JP2003041329A (en) 2003-02-13
JP4180836B2 (en) 2008-11-12
FR2824845A1 (en) 2002-11-22

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