EP2374135A2 - Method for processing a nitrous aqueous liquid effluent by calcination and vitrification - Google Patents

Method for processing a nitrous aqueous liquid effluent by calcination and vitrification

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Publication number
EP2374135A2
EP2374135A2 EP09799361A EP09799361A EP2374135A2 EP 2374135 A2 EP2374135 A2 EP 2374135A2 EP 09799361 A EP09799361 A EP 09799361A EP 09799361 A EP09799361 A EP 09799361A EP 2374135 A2 EP2374135 A2 EP 2374135A2
Authority
EP
European Patent Office
Prior art keywords
nitrate
calcination
effluent
expressed
oxides
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP09799361A
Other languages
German (de)
French (fr)
Other versions
EP2374135B1 (en
Inventor
Alain Ledoux
Jean-François HOLLEBECQUE
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Orano Demantelement SAS
Original Assignee
Areva NC SA
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Publication date
Application filed by Areva NC SA filed Critical Areva NC SA
Publication of EP2374135A2 publication Critical patent/EP2374135A2/en
Application granted granted Critical
Publication of EP2374135B1 publication Critical patent/EP2374135B1/en
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Classifications

    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/28—Treating solids
    • G21F9/30—Processing
    • G21F9/301—Processing by fixation in stable solid media
    • G21F9/302—Processing by fixation in stable solid media in an inorganic matrix
    • G21F9/305—Glass or glass like matrix
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/04—Treating liquids
    • G21F9/06—Processing
    • G21F9/14—Processing by incineration; by calcination, e.g. desiccation
    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/28—Treating solids
    • G21F9/30—Processing

Definitions

  • the invention relates to a method for treating an aqueous nitrate liquid effluent containing nitrates of metals or metalloids, which comprises a calcination step generally followed by a vitrification step of the calcine obtained during said calcination step.
  • the nitric aqueous liquid effluent may contain mainly sodium nitrate.
  • the technical field of the invention can be defined generally as that of the calcination of liquid effluents, more particularly the technical field of the invention can be defined as the calcination of radioactive liquid effluents for their vitrification.
  • the French vitrification process for radioactive liquid effluents comprises two steps.
  • the first step is a step of calcining the effluent during which a drying and then a denitration of a portion of the nitrates takes place.
  • the second step is a vitrification step by dissolving in a glass of containment the calcine produced during the calcination step.
  • the calcination step is generally carried out in a rotary tube heated by an oven electric.
  • the solid calcine is ground by an idle bar placed inside the rotating tube.
  • the aluminum content in the glass must not be too high and is generally limited to about 15% by weight expressed as Al 2 O 3.
  • This method of treating a nitric aqueous effluent by calcination must of course be able to be implemented reliably, reproducibly, regardless of the treated effluent and dilution adjuvant implemented.
  • the object of the present invention is to provide a method for treating an aqueous nitrate liquid effluent containing nitrates of metals or metalloids, this process comprising a step of calcining the effluent to transform the nitrates of metals or metalloids into their oxides, which, among other things, meet the needs mentioned above.
  • the object of the present invention is still to provide such a method which does not have the disadvantages, limitations, defects and disadvantages of the processes of the prior art and which solves the problems of the processes of the prior art, in particular with regard to the determination of the operating parameters of the process and the optimization of the amount of dilution adjuvant to be added to the effluent.
  • a method of treating an aqueous nitrate liquid effluent containing nitrates of metals or metalloids comprising a step of calcining the effluent to transform the nitrates of metals or metalloids to oxides of metals or metalloids, at least one compound selected from nitrates of metals or metalloids and other compounds of the effluent resulting in calcination with a sticky oxide, and a dilution adjuvant comprising at least one metal or metalloid nitrate resulting in calcination with a non - sticky oxide being added to the effluent prior to the calcination step to give a mixture of effluent and dilution adjuvant, wherein mixture checks the two following inequations (I ' (2):
  • the mass of all compounds in the mixture could possibly be simplified and replaced by the mass of all the salts of the mixture, including nitrates, expressed in terms of oxides.
  • the denominator could be further possibly simplified in both inequations (1) and (2) and replaced by the mass of nitrates of the mixture, expressed in terms of oxides.
  • the mass of all the compounds of the mixture leading, when calcined, to sticky oxides, expressed in terms of oxides could possibly be simplified and replaced by the mass of nitrates. and other compounds of the mixture which, upon calcination, are obtained with sticky oxides, expressed in terms of oxides, since the tacky compounds may generally comprise tacky nitrates and other tacky compounds or only other tacky compounds.
  • the numerator could possibly be further simplified and replaced by the mass of nitrates in the mixture, which, when calcined, leads to sticky oxides, expressed in terms of oxides.
  • the process according to the invention is fundamentally defined by the fact that the addition of the dilution adjuvant chosen from the nitrates of metals or metalloids leading during their calcination to so-called non-sticky oxides, is governed by both inequations (1) (2) mentioned above.
  • the dilution adjuvant supply was such that both inequalities were verified, then the calcination of the effluent was possible without any the walls of the calciner, nor any clogging thereof.
  • the simple application of this very simple criterion for the addition of the dilution adjuvant, based on the above inequalities, reliably avoids the calciner clogging phenomena.
  • a single calcination test regardless of the effluent, makes it possible to optimize the characteristics of the calcine, in particular as regards its granulometry, by simply playing on the heating and on the content of calcination adjuvant, which is generally sugar.
  • This simple, reliable criterion is of general application irrespective of the treated effluent generally containing mainly sodium nitrate and the nature of the other sticky and non-sticky compounds contained therein. This criterion also applies regardless of the nature and number of compounds, nitrates, added to the effluent as dilution adjuvants.
  • the dilution adjuvant comprises aluminum nitrate and optionally at least one other nitrate of metal or metalloid, this (s) nitrate (s) leading during calcination to at least one non-sticky oxide.
  • This at least one other metal or metalloid nitrate is generally selected from iron nitrate and rare earth nitrates.
  • iron nitrate and rare earth nitrates have calcination bonding properties close to those of nitrate d aluminum, and that the oxides from these specific nitrates, which are so-called “non-sticky” oxides, can also dissolve in the final glass produced during the subsequent vitrification step.
  • a dilution adjuvant preferably comprising a substitution of a portion of the aluminum nitrate, a nitrate selected from iron nitrate and rare earth nitrates thus makes it possible to avoid clogging of the tube of the calcination apparatus during the calcination of effluents generating very tacky oxides, such as solutions with a high sodium content, while minimizing the increase in the quantity of confining glass to be produced during the vitrification step which usually follows calcination.
  • iron nitrate and rare earth nitrates have all the excellent properties of nitrate aluminum as to its ability to limit the bonding of calcine, and thus to prevent clogging of the calcination tube, while allowing to increase the rate of charge of the waste and thus to limit the amount of glass to produce.
  • the constraints imposed on the glass formulation by the preferred dilution adjuvants according to the invention comprising a specific nitrate selected from iron nitrate and rare earth nitrates are significantly reduced compared to dilution adjuvants consisting solely of aluminum nitrate of made of the lower aluminum intake.
  • Iron and rare earth nitrates thus provide an additional advantage during vitrification, in addition to the surprising effects and advantages due to the application according to the process of the invention of the criteria (1) (2) defined above. high.
  • Rare earth nitrates are lanthanum nitrate, cerium nitrate, praseodymium nitrate, neodymium nitrate.
  • the dilution adjuvant may thus comprise aluminum nitrate and optionally at least one other nitrate selected from iron nitrate, lanthanum nitrate, cerium nitrate, praseodymium nitrate and neodymium nitrate.
  • each of the nitrates is free from the point of view of their effectiveness to prevent calcine sticking in the tube and can therefore be adjusted according to their impact on the properties of the confinement glass prepared in a subsequent vitrification step.
  • the amount of dilution adjuvant added to the liquid effluent is determined by applying both inequations (1) and (2).
  • the effluent is a nitric solution usually containing mainly sodium nitrate and other constituents such as nitrates
  • the effluent may also contain "sticky” or “non-sticky” compounds which are not nitrates, generally present in the form of salts, such as phosphomolybdic acid which is a so-called “sticky” compound.
  • the process according to the invention allows the calcination without clogging of all kinds of effluents, whatever their nature, and the nature of the nitrates and nitrates sticky contained therein.
  • the liquid effluent treated by the process according to the invention contains at least one compound such as a metal or metalloid nitrate leading, during calcination, to a so-called “sticky” oxide, and / or at least one other compound which is not such a nitrate leading during calcination to a so-called "sticky” oxide.
  • sticky compounds means compounds, oxides, nitrates known to stick to the walls of "calciner” calcination apparatus and induce clogging phenomena of these calcinators.
  • the compound (s) such as the nitrate (s) and / or the other compound (s) which conduct (conduct) during calcination to an oxide (s) whether sticky (s) could they be sodium nitrate, phosphomolybdic acid or boron nitrate or mixtures thereof.
  • the content of this or these compound (s) such as the "sticky” nitrate (s) and / or other "sticky” compounds in the effluent, expressed in oxides, relative to the mass total of nitrates contained in the effluent, also expressed in oxides, is generally greater than 35% by weight, or greater than 30% by weight for the sodium nitrate expressed in oxides.
  • the process according to the invention makes it possible in particular to calcinate effluents with a high content of compounds such as nitrates and other so-called "sticky" compounds, ie greater than 35% by weight for all of the "sticky" nitrates, or greater than 30% by weight, for sodium nitrate.
  • the process according to the invention allows the calcination of high sodium solutions which are very tacky.
  • the effluent has a sodium nitrate content, expressed as sodium oxide, relative to the total mass of the nitrates (or possibly, more precisely , relative to the total mass of salts) contained in the effluent, expressed in oxides of greater than 30% by weight, preferably greater than 50% by weight.
  • a single calcination test makes it possible to optimize the characteristics. calcinates by varying the heating of the different calciner zones, the calcination aid content (generally) and the rotational speed of the calciner tube.
  • the conditions for calcination are generally as follows: temperature reached by the calcine of about 400 0 C.
  • This calcination step is generally carried out in a heated rotating tube, preferably up to the desired temperature indicated above, for example by an electric furnace with several independent heating zones.
  • Heating zones are more particularly dedicated to evaporation and others to calcination.
  • the calcination zones make it possible to heat the calcine at the temperature of 400 ° C.
  • the calcination step is carried out at a furnace calcine temperature of about 400 ° C.
  • the treatment process according to the invention generally comprises, after the calcination step, a vitrification step of the calcine obtained during this calcination step.
  • This vitrification step consists of a reaction between the calcine and a glass frit (preformed glass) to obtain a confinement glass.
  • a vitrification step is performed which consists in developing a confinement glass from the melting of the calcine from the calcination step with glass frit.
  • the implementation preferably in the dilution adjuvant of iron and rare earth-specific nitrates also advantageously makes it possible to relax the constraints with regard to the formulation of the glass.
  • a higher proportion of effluent in the glass can be incorporated when the calcine was obtained using the dilution adjuvant according to the invention in place of a dilution adjuvant consisting solely of aluminum nitrate.
  • the high intake of aluminum in the case of a dilution admixture consisting solely of aluminum nitrate tends to harden the calcine and has the consequence of causing a decrease in the reactivity between the calcine and the frit of glass in the vitrification furnace.
  • Vitrification consists of a melting reaction between the calcine and the glass frit to form a confining glass. It is made in two types of ovens: indirect induction ovens which consists of heating by four inductors a metal pot into which the sintered / calcined mixture is introduced, and the direct induction furnaces which consist in heating the glass by an inductor through a cooled structure (cold crucible) which allows part of the electromagnetic field and in which is introduced continuously the sintered mixture / calcinate.
  • indirect induction ovens which consists of heating by four inductors a metal pot into which the sintered / calcined mixture is introduced
  • the direct induction furnaces which consist in heating the glass by an inductor through a cooled structure (cold crucible) which allows part of the electromagnetic field and in which is introduced continuously the sintered mixture / calcinate.
  • Example 1 In this example, the calcination of an effluent containing a high content of sodium nitrate is described.
  • composition of this effluent is given in Table 1, this composition being expressed in% by weight of the oxides corresponding to the salts contained in the effluent, which are nitrates.
  • the percentage of oxides is expressed in relation to the total mass of the oxides corresponding to the salts contained in the effluent.
  • the effluent described in Table 1 below is very charged especially in sodium and therefore very sticky.
  • an adjuvant (adjuvant 1) is added to the effluent of Table 1 which consists of 100% by weight of aluminum nitrate, expressed as Al 2 O 3 oxide, at the rate of 95.05% by weight of adjuvant expressed as oxide for 100% in mass of effluent expressed in% by weight of the oxides corresponding to the salts contained in the effluent. It should be noted that the amount of adjuvant has been minimized by applying the criteria according to the invention.
  • the conditions of calcination are as follows:
  • the temperature reached by the calcine is about 400 ° C.
  • the speed of rotation of the rotating tube containing the idler bar is 20 rpm
  • the calcination aid content is 40 g / L of the effluent mixture with the dilution adjuvant.
  • adjuvant 2 preferred according to the invention which consists of 75% by weight of aluminum nitrate expressed as Al 2 O 3 oxide and 25% by weight of iron nitrate expressed as Fe 2 O 3 oxide. This adjuvant is added in the same amount as the adjuvant 1 determined by the same calculations on the basis of the criteria according to the invention.
  • Example 1 the vitrification of the calcine obtained in Example 1 is carried out.
  • calcine was prepared using an adjuvant ("adjuvant No. 1") consisting solely of aluminum nitrate.
  • adjuvant No. 1 consisting solely of aluminum nitrate.
  • the range of glass composition that we were able to develop requires a maximum alumina content of 13% by weight in the glass.
  • the glass is made from calcine and a glass frit containing 1% by weight of alumina.
  • the vitrification was carried out in a cold crucible at 1230 ° C.
  • Example 4 In this example, the vitrification of the calcine obtained in Example 2 is carried out. It should be remembered that this calcine was prepared using a preferred adjuvant ("adjuvant # 2") consisting of 75% by weight of sodium salt. aluminum and 25% by weight of iron salt.
  • adjuvant # 2 a preferred adjuvant
  • the high intake of aluminum by the adjuvant No. 1 tends to harden the calcine and results in a slight decrease in reactivity between the calcine and the glass frit in the vitrification furnace.
  • a builder (adjuvant 1) of the prior art which consists of 100% by weight of aluminum nitrate expressed as Al 2 O 3 oxide.
  • adjuvant 3 the adjuvant according to the invention in which part of the aluminum nitrate is replaced by nitrates of lanthanum, cerium, neodymium and praseodymium.
  • the minimum content of dilution adjuvant to be added to this effluent consisting solely of sodium nitrate expressed as total oxide mass represents 70% in the mixture of the effluent with the dilution adjuvant.
  • the conditions of calcination are as follows: Calcinator with two independent heating zones, the temperature reached by the calcine is approximately 400 ° C., the speed of rotation of the rotating tube containing the idler bar is 35 rpm, the calcination aid content is 20 g / L of the effluent mixture with the dilution adjuvant.

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  • Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Glass Melting And Manufacturing (AREA)
  • Removal Of Specific Substances (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Treating Waste Gases (AREA)

Abstract

The invention relates to a method for processing a nitrous aqueous liquid effluent containing nitrates of metals or metalloids, including the step of calcinating the effluent in order to convert the metal or metalloid nitrates into metal or metalloid oxides, at least one compound selected from the metal or metalloid nitrates and the other compounds of the effluent resulting in a sticky oxide upon calcination, and a dilution additive including at least one metal or metalloid nitrate resulting in a non-sticky oxide upon calcination being added to the effluent prior to the calcination step in order to provide a mixture of effluent and dilution additive.

Description

PROCEDE DE TRAITEMENT D'UN EFFLUENT LIQUIDE AQUEUX NITRIQUE PAR CALCINATION ET VITRIFICATION PROCESS FOR TREATING NITRIC AQUEOUS LIQUID EFFLUENT BY CALCINATION AND VITRIFICATION
DESCRIPTIONDESCRIPTION
L' invention concerne un procédé de traitement d'un effluent liquide aqueux nitrique contenant des nitrates de métaux ou de métalloïdes, qui comprend une étape de calcination généralement suivie d'une étape de vitrification du calcinât obtenu lors de ladite étape de calcination. L' effluent liquide aqueux nitrique peut contenir majoritairement du nitrate de sodium.The invention relates to a method for treating an aqueous nitrate liquid effluent containing nitrates of metals or metalloids, which comprises a calcination step generally followed by a vitrification step of the calcine obtained during said calcination step. The nitric aqueous liquid effluent may contain mainly sodium nitrate.
Le domaine technique de l'invention peut être défini de manière générale comme celui de la calcination des effluents liquides, plus particulièrement le domaine technique de l'invention peut être défini comme celui de la calcination des effluents liquides radioactifs en vue de leur vitrification.The technical field of the invention can be defined generally as that of the calcination of liquid effluents, more particularly the technical field of the invention can be defined as the calcination of radioactive liquid effluents for their vitrification.
Le procédé français de vitrification des effluents liquides radioactifs comporte deux étapes. La première étape est une étape de calcination de 1' effluent au cours de laquelle se produit un séchage puis une dénitration d'une partie des nitrates, la deuxième étape est une étape de vitrification par dissolution dans un verre de confinement du calcinât produit lors de l'étape de calcination.The French vitrification process for radioactive liquid effluents comprises two steps. The first step is a step of calcining the effluent during which a drying and then a denitration of a portion of the nitrates takes place. The second step is a vitrification step by dissolving in a glass of containment the calcine produced during the calcination step.
L'étape de calcination est généralement effectuée dans un tube tournant chauffé par un four électrique. Le calcinât solide est broyé par une barre folle placée à l'intérieur du tube tournant.The calcination step is generally carried out in a rotary tube heated by an oven electric. The solid calcine is ground by an idle bar placed inside the rotating tube.
Lors de la calcination de certaines solutions, en particulier des solutions riches en nitrate de sodium autrement dit des solutions à forte teneur en sodium en milieu nitrique, on peut observer un collage du calcinât sur les parois du tube tournant pouvant conduire à un colmatage total du tube du calcinateur . La parade a consisté à ajouter à l'effluent un composé réputé non collant dénommé adjuvant de dilution tel que le nitrate d'aluminium, pour permettre leur calcination en évitant le colmatage du calcinateur . Mais, la quantité d'adjuvant de calcination par exemple de nitrate d'aluminium à ajouter est difficile à optimiser. Ainsi pour chaque nouvel effluent, plusieurs essais sont nécessaires pour déterminer les conditions opératoires de calcination en tube tournant chauffé permettant d'éviter les colmatages de tube. Il faut notamment ajuster la chauffe du four de calcination et les quantités d'adjuvant de calcination, qui est différent de l'adjuvant de dilution, et qui est généralement du sucre.During the calcination of certain solutions, in particular solutions rich in sodium nitrate, in other words solutions with a high sodium content in a nitric medium, it is possible to observe a bonding of the calcine on the walls of the rotating tube which can lead to a total clogging of the calciner tube. The parry was to add to the effluent a deemed non-sticky compound called dilution adjuvant such as aluminum nitrate, to allow their calcination by avoiding the clogging of the calciner. However, the amount of calcination aid, for example aluminum nitrate to be added, is difficult to optimize. Thus, for each new effluent, several tests are necessary to determine the operating conditions of heated rotating tube calcination to prevent clogging of the tube. In particular, it is necessary to adjust the heating of the calcination furnace and the quantities of calcination aid, which is different from the dilution adjuvant, and which is generally sugar.
En outre dans le cas du nitrate d'aluminium, son addition à l'effluent augmente la quantité de verre à produire. En effet, la présence d' alumine dans le verre augmente sa température d'élaboration et conduit à limiter le taux de charge en déchet, effluent dans le verre, pour ne pas dégrader les propriétés de confinement de ce verre.In addition, in the case of aluminum nitrate, its addition to the effluent increases the quantity of glass to be produced. Indeed, the presence of alumina in the glass increases its production temperature and leads to limit the charge rate in waste, effluent in the glass, so as not to degrade the confinement properties of this glass.
La teneur en aluminium dans le verre ne doit donc pas être trop importante et est généralement limitée à environ 15% en masse exprimé en AI2O3.The aluminum content in the glass must not be too high and is generally limited to about 15% by weight expressed as Al 2 O 3.
Il existe donc un besoin au regard de ce qui précède pour un procédé de traitement par calcination d'un effluent aqueux nitrique contenant des composés tels que des nitrates de métaux ou de métalloïdes et d'autres composés, susceptibles de former des oxydes collants lors de leur calcination, dans lequel les conditions opératoires permettant d'éviter le collage du calcinât sur les parois du tube de calcination peuvent être déterminés simplement par un nombre limité d'essais de calcination.There is therefore a need in view of the foregoing for a treatment process by calcination of a nitric aqueous effluent containing compounds such as nitrates of metals or metalloids and other compounds, likely to form sticky oxides during their calcination, in which the operating conditions for avoiding calcine bonding on the walls of the calcination tube can be determined simply by a limited number of calcination tests.
Plus précisément, il existe un besoin pour un tel procédé dans lequel la quantité d'adjuvant de dilution à ajouter à l' effluent préalablement à la calcination, peut être déterminée de manière simple, fiable, par un nombre réduit d'essais, permettant ainsi d'optimiser et de réduire au minimum la quantité d'adjuvant de dilution à ajouter à l' effluent .More specifically, there is a need for such a process in which the amount of dilution adjuvant to be added to the effluent prior to calcination can be determined simply, reliably, by a limited number of tests, thus allowing optimize and minimize the amount of dilution adjuvant to add to the effluent.
Ce procédé de traitement d'un effluent aqueux nitrique par calcination doit bien sûr pouvoir être mis en œuvre de manière fiable, reproductible, quel que soit l' effluent traité et l'adjuvant de dilution mis en œuvre.This method of treating a nitric aqueous effluent by calcination must of course be able to be implemented reliably, reproducibly, regardless of the treated effluent and dilution adjuvant implemented.
En outre, il serait également souhaitable que ce procédé limite en outre l'augmentation de la quantité de verre de confinement à produire lors de la vitrification du calcinât. Le but de la présente invention est de fournir un procédé de traitement d'un effluent liquide aqueux nitrique contenant des nitrates de métaux ou de métalloïdes, ce procédé comprenant une étape de calcination de l' effluent pour transformer les nitrates de métaux ou de métalloïdes en leurs oxydes qui répondent entre autres aux besoins mentionnés plus haut .In addition, it would also be desirable for this process to further limit the increase in the amount of confining glass to be produced during vitrification of the calcine. The object of the present invention is to provide a method for treating an aqueous nitrate liquid effluent containing nitrates of metals or metalloids, this process comprising a step of calcining the effluent to transform the nitrates of metals or metalloids into their oxides, which, among other things, meet the needs mentioned above.
Le but de la présente invention est encore de fournir un tel procédé qui ne présente pas les inconvénients, limitations, défauts et désavantages des procédés de l'art antérieur et qui résolve les problèmes des procédés de l'art antérieur, notamment en ce qui concerne la détermination des paramètres opératoires du procédé et l'optimisation de la quantité d'adjuvant de dilution à ajouter à l' effluent .The object of the present invention is still to provide such a method which does not have the disadvantages, limitations, defects and disadvantages of the processes of the prior art and which solves the problems of the processes of the prior art, in particular with regard to the determination of the operating parameters of the process and the optimization of the amount of dilution adjuvant to be added to the effluent.
Ce but, et d'autres encore, sont atteints, conformément à l'invention par un procédé de traitement d'un effluent liquide aqueux nitrique contenant des nitrates de métaux ou de métalloïdes, comprenant une étape de calcination de l' effluent pour transformer les nitrates de métaux ou de métalloïdes en oxydes des métaux ou métalloïdes, au moins un composé choisi parmi les nitrates de métaux ou de métalloïdes et les autres composés de l' effluent conduisant lors de la calcination à un oxyde collant, et un adjuvant de dilution comprenant au moins un nitrate de métal ou de métalloïde conduisant lors de la calcination à un oxyde non collant étant ajouté à l' effluent préalablement à l'étape de calcination pour donner un mélange d' effluent et d'adjuvant de dilution, dans lequel le mélange vérifie les deux inéquations suivantes (I' (2) :This and other objects are achieved in accordance with the invention by a method of treating an aqueous nitrate liquid effluent containing nitrates of metals or metalloids, comprising a step of calcining the effluent to transform the nitrates of metals or metalloids to oxides of metals or metalloids, at least one compound selected from nitrates of metals or metalloids and other compounds of the effluent resulting in calcination with a sticky oxide, and a dilution adjuvant comprising at least one metal or metalloid nitrate resulting in calcination with a non - sticky oxide being added to the effluent prior to the calcination step to give a mixture of effluent and dilution adjuvant, wherein mixture checks the two following inequations (I ' (2):
masse de nitrate de sodium du mélange exprimée en termes d'oxyde Na2O ^ n - masse de tous les composés du mélange exprimée en termes d'oxydesSodium nitrate mass of the mixture expressed in terms of oxide Na 2 O 3 n - mass of all the compounds of the mixture expressed in terms of oxides
masse de tous les composés du mélange conduisant lors de leur calcination à . _ . des oxydes collants, exprimée en termes d'oxydes masse de tous les composés du mélange exprimée en termes d'oxydesmass of all the compounds of the mixture leading to calcination at. _. sticky oxides, expressed in terms of the mass oxides of all the compounds of the mixture expressed in terms of oxides
Dans l'une ou l'autre ou les deux inéquations (1) et (2), au dénominateur, la masse de tous les composés du mélange, exprimée en termes d'oxydes, pourrait être éventuellement simplifiée et remplacée par la masse de tous les sels du mélange, y compris les nitrates, exprimée en termes d'oxydes. Le dénominateur pourrait être encore éventuellement simplifié dans les deux inéquations (1) et (2) et remplacé par la masse des nitrates du mélange, exprimée en termes d'oxydes.In either one or both (1) and (2) inequations, the mass of all compounds in the mixture, expressed in terms of oxides, could possibly be simplified and replaced by the mass of all the salts of the mixture, including nitrates, expressed in terms of oxides. The denominator could be further possibly simplified in both inequations (1) and (2) and replaced by the mass of nitrates of the mixture, expressed in terms of oxides.
En outre, dans l'inéquation (2), au numérateur, la masse de tous les composés du mélange conduisant lors de leur calcination à des oxydes collants, exprimée en termes d'oxydes, pourrait être éventuellement simplifiée et remplacée par la masse des nitrates et autres composés du mélange conduisant lors de leur calcination à des oxydes collants, exprimée en termes d'oxydes, car les composés collants peuvent comprendre généralement des nitrates collants et d'autres composés collants ou seulement d'autres composés collants. Dans l'inéquation (2), le numérateur pourrait être encore éventuellement simplifié et remplacé par la masse des nitrates du mélange conduisant lors de leur calcination à des oxydes collants, exprimée en termes d'oxydes.In addition, in the equation (2), in the numerator, the mass of all the compounds of the mixture leading, when calcined, to sticky oxides, expressed in terms of oxides, could possibly be simplified and replaced by the mass of nitrates. and other compounds of the mixture which, upon calcination, are obtained with sticky oxides, expressed in terms of oxides, since the tacky compounds may generally comprise tacky nitrates and other tacky compounds or only other tacky compounds. In inequation (2), the numerator could possibly be further simplified and replaced by the mass of nitrates in the mixture, which, when calcined, leads to sticky oxides, expressed in terms of oxides.
La forme la plus simplifiée des deux inéquations (1) et (2) est donc la suivante :The most simplified form of the two inequations (1) and (2) is therefore the following:
masse de nitrate de sodium du mélange exprimée en termes d'oxyde Na2O ^ n - masse de tous les nitrates du mélange exprimée en termes d'oxydesSodium nitrate mass of the mixture expressed in terms of oxide Na 2 O 3 n - mass of all the nitrates of the mixture expressed in terms of oxides
masse des nitrates du mélange conduisant lors de leur calcination à des oxydes collants, exprimée en termes d'oxydes masse de tous les nitrates du mélange exprimée en termes d'oxydesmass of the nitrates of the mixture leading, during their calcination, to sticky oxides, expressed in terms of the mass oxides of all the nitrates of the mixture, expressed in terms of oxides
Ces deux inéquations (1) (2) ou (1') (2') sont d'application générale quel que soit notamment l'adjuvant de dilution.These two inequations (1) (2) or (1 ') (2') are of general application whatever the dilution adjuvant.
Le procédé selon l'invention est de manière fondamentale défini par le fait que l'addition de l'adjuvant de dilution choisi parmi les nitrates de métaux ou de métalloïdes conduisant lors de leur calcination à des oxydes dits non collants, est régie par les deux inéquations (1) (2) mentionnées plus haut. Il a été mis en évidence, de manière surprenante, selon l'invention, que lorsque l'apport en adjuvant de dilution était tel que les deux inéquations étaient vérifiées alors la calcination de l'effluent, était possible sans que se produise aucun collage sur les parois de l'appareil de calcination, ni aucun colmatage de celui-ci. La simple application de ce critère très simple pour l'addition de l'adjuvant de dilution, basé sur les inéquations ci-dessus, permet de manière fiable d'éviter avec sûreté les phénomènes de colmatage des calcinateurs .The process according to the invention is fundamentally defined by the fact that the addition of the dilution adjuvant chosen from the nitrates of metals or metalloids leading during their calcination to so-called non-sticky oxides, is governed by both inequations (1) (2) mentioned above. Surprisingly, according to the invention, it was demonstrated that when the dilution adjuvant supply was such that both inequalities were verified, then the calcination of the effluent was possible without any the walls of the calciner, nor any clogging thereof. The simple application of this very simple criterion for the addition of the dilution adjuvant, based on the above inequalities, reliably avoids the calciner clogging phenomena.
Un seul essai de calcination, et ce quel que soit l'effluent, permet d'optimiser les caractéristiques du calcinât notamment quant à sa granulométrie, en jouant simplement sur la chauffe et sur la teneur en adjuvant de calcination qui est généralement le sucre.A single calcination test, regardless of the effluent, makes it possible to optimize the characteristics of the calcine, in particular as regards its granulometry, by simply playing on the heating and on the content of calcination adjuvant, which is generally sugar.
Selon l'invention, on a donc pu définir un critère massique très simple pour déterminer l'apport d'adjuvant de dilution, qui permet de minimiser a priori, préalablement à la calcination, la quantité d'adjuvant à ajouter à l'effluent pour éviter tout colmatage .According to the invention, it has therefore been possible to define a very simple mass criterion for determining the supply of dilution adjuvant, which makes it possible to minimize a priori, prior to calcination, the amount of adjuvant to be added to the effluent for avoid clogging.
Ce critère simple, fiable, est d'application générale quel que soit l'effluent traité contenant généralement majoritairement du nitrate de sodium et la nature des autres composés collants et non collants qui s'y trouvent contenus. Ce critère s'applique également quels que soient la nature et le nombre des composés, nitrates, ajoutés à l'effluent en tant qu'adjuvants de dilution.This simple, reliable criterion is of general application irrespective of the treated effluent generally containing mainly sodium nitrate and the nature of the other sticky and non-sticky compounds contained therein. This criterion also applies regardless of the nature and number of compounds, nitrates, added to the effluent as dilution adjuvants.
L'adjuvant de dilution comprend du nitrate d'aluminium et éventuellement au moins un autre nitrate de métal ou de métalloïde, ce (s) nitrate (s) conduisant lors de la calcination à au moins un oxyde non collant. Ce au moins un autre nitrate de métal ou de métalloïde est généralement choisi parmi le nitrate de fer et les nitrates de terres rares.The dilution adjuvant comprises aluminum nitrate and optionally at least one other nitrate of metal or metalloid, this (s) nitrate (s) leading during calcination to at least one non-sticky oxide. This at least one other metal or metalloid nitrate is generally selected from iron nitrate and rare earth nitrates.
L'utilisation de nitrate de fer ou d'un nitrate de terre rare dans un adjuvant de dilution ajouté à un effluent liquide aqueux nitrique préalablement à la calcination de cet effluent n'a, jusqu'alors, jamais été mentionnée, ni évoquée.The use of iron nitrate or rare earth nitrate in a dilution adjuvant added to a liquid aqueous nitrate effluent prior to the calcination of this effluent has hitherto never been mentioned or mentioned.
Parmi les nitrates de l'adjuvant de dilution cités ci-dessus, il s'est avéré que, de manière étonnante, le nitrate de fer et les nitrates de terres rares possédaient des propriétés de limitation du collage du calcinât proches de celles du nitrate d'aluminium, et que les oxydes issus de ces nitrates spécifiques, qui sont des oxydes dits « non collants », peuvent se dissoudre également dans le verre final produit lors de l'étape de vitrification ultérieure.Among the nitrates of the dilution adjunct mentioned above, it has been found that, surprisingly, iron nitrate and rare earth nitrates have calcination bonding properties close to those of nitrate d aluminum, and that the oxides from these specific nitrates, which are so-called "non-sticky" oxides, can also dissolve in the final glass produced during the subsequent vitrification step.
La mise en œuvre d'un adjuvant de dilution comprenant de préférence en substitution d'une partie du nitrate d'aluminium, un nitrate choisi parmi le nitrate de fer et les nitrates de terres rares permet donc d'éviter le colmatage du tube de l'appareil de calcination lors de la calcination d'effluents générant des oxydes très collants, tels que les solutions à forte teneur en sodium, tout en minimisant l'augmentation de la quantité de verre de confinement à produire lors de l'étape de vitrification qui suit généralement la calcination.The use of a dilution adjuvant preferably comprising a substitution of a portion of the aluminum nitrate, a nitrate selected from iron nitrate and rare earth nitrates thus makes it possible to avoid clogging of the tube of the calcination apparatus during the calcination of effluents generating very tacky oxides, such as solutions with a high sodium content, while minimizing the increase in the quantity of confining glass to be produced during the vitrification step which usually follows calcination.
On peut dire que, de manière surprenante, le nitrate de fer et les nitrates de terres rares présentent toutes les excellentes propriétés du nitrate d'aluminium quant à sa capacité à limiter le collage du calcinât, et donc à éviter le colmatage du tube de calcination, tout en permettant d'augmenter le taux de charge du déchet et donc de limiter la quantité de verre à produire.Surprisingly, iron nitrate and rare earth nitrates have all the excellent properties of nitrate aluminum as to its ability to limit the bonding of calcine, and thus to prevent clogging of the calcination tube, while allowing to increase the rate of charge of the waste and thus to limit the amount of glass to produce.
Les contraintes imposées sur la formulation verrière par les adjuvants de dilution préférés selon l'invention comprenant un nitrate spécifique choisi parmi le nitrate de fer et les nitrates de terres rares sont nettement réduites par rapport aux adjuvants de dilution constitués uniquement de nitrate d'aluminium du fait de l'apport plus faible en aluminium.The constraints imposed on the glass formulation by the preferred dilution adjuvants according to the invention comprising a specific nitrate selected from iron nitrate and rare earth nitrates are significantly reduced compared to dilution adjuvants consisting solely of aluminum nitrate of made of the lower aluminum intake.
Les nitrates de fer et de terres rares, apportent donc un avantage supplémentaire lors de la vitrification qui vient s'ajouter aux effets et avantages surprenant dus à l'application conformément au procédé de l'invention des critères (1) (2) définis plus haut.Iron and rare earth nitrates thus provide an additional advantage during vitrification, in addition to the surprising effects and advantages due to the application according to the process of the invention of the criteria (1) (2) defined above. high.
Les nitrates de terres rares sont le nitrate de lanthane, le nitrate de cérium, le nitrate de praséodyme, le nitrate de néodyme.Rare earth nitrates are lanthanum nitrate, cerium nitrate, praseodymium nitrate, neodymium nitrate.
L'adjuvant de dilution pourra ainsi comprendre du nitrate d'aluminium et éventuellement au moins un autre nitrate choisi parmi le nitrate de fer, le nitrate de lanthane, le nitrate de cérium, le nitrate de praséodyme et le nitrate de néodyme.The dilution adjuvant may thus comprise aluminum nitrate and optionally at least one other nitrate selected from iron nitrate, lanthanum nitrate, cerium nitrate, praseodymium nitrate and neodymium nitrate.
La quantité respective de chacun des nitrates est libre du point de vue de leur efficacité pour empêcher le collage du calcinât dans le tube et peut donc être ajustée en fonction de leur impact sur les propriétés du verre de confinement préparé dans une étape ultérieure de vitrification.The respective amount of each of the nitrates is free from the point of view of their effectiveness to prevent calcine sticking in the tube and can therefore be adjusted according to their impact on the properties of the confinement glass prepared in a subsequent vitrification step.
La quantité d'adjuvant de dilution ajoutée à l'effluent liquide est déterminée en appliquant les deux inéquations (1) et (2) .The amount of dilution adjuvant added to the liquid effluent is determined by applying both inequations (1) and (2).
L'effluent est une solution nitrique contenant généralement majoritairement du nitrate de sodium et d'autres constituants tels que des nitratesThe effluent is a nitric solution usually containing mainly sodium nitrate and other constituents such as nitrates
(y compris les nitrates contenus dans l'adjuvant de dilution) .(including the nitrates contained in the dilution adjuvant).
L'effluent peut également contenir des composés « collants » ou « non collants » qui ne sont pas des nitrates, généralement présents sous forme de sels, tels que l'acide phosphomolybdique qui est un composé dit « collant ».The effluent may also contain "sticky" or "non-sticky" compounds which are not nitrates, generally present in the form of salts, such as phosphomolybdic acid which is a so-called "sticky" compound.
Le procédé selon l'invention permet la calcination sans colmatage de toutes sortes d'effluents, quelle que soit leur nature, et la nature des nitrates et nitrates collants qui s'y trouvent contenus.The process according to the invention allows the calcination without clogging of all kinds of effluents, whatever their nature, and the nature of the nitrates and nitrates sticky contained therein.
L'effluent liquide traité par le procédé selon l'invention contient au moins un composé tel qu'un nitrate de métal ou de métalloïde conduisant lors de la calcination à un oxyde dit « collant », et/ou au moins un autre composé qui n'est pas un tel nitrate conduisant lors de la calcination à un oxyde dit « collant ».The liquid effluent treated by the process according to the invention contains at least one compound such as a metal or metalloid nitrate leading, during calcination, to a so-called "sticky" oxide, and / or at least one other compound which is not such a nitrate leading during calcination to a so-called "sticky" oxide.
Dans la présente description, on utilise les termes « composés collants », « oxydes collants » ou bien « nitrates collants ». On entend par « composés collants », « nitrates collants » ou « oxydes collants » les composés, oxydes, nitrates connus pour se coller aux parois des appareils de calcination « calcinateur » et induire des phénomènes de colmatage de ces calcinateurs .In the present description, the terms "sticky compounds", "sticky oxides" or "sticky nitrates" are used. The term "sticky compounds", "sticky nitrates" or "sticky oxides" means compounds, oxides, nitrates known to stick to the walls of "calciner" calcination apparatus and induce clogging phenomena of these calcinators.
Les termes « composé collant », « oxyde collant », « nitrate collant » sont des termes couramment utilisés dans ce domaine de la technique, qui ont une signification bien établie, qui sont connus de l'homme du métier et ne présentent pour lui aucune ambiguïté .The terms "sticky compound", "sticky oxide", "sticky nitrate" are terms commonly used in this field of the art, which have a well-established meaning, which are known to those skilled in the art and do not present for him any ambiguity.
Ainsi, le ou les composé (s) tel (s) que le ou les nitrate (s) et/ou le ou les autres composé (s) qui conduit (conduisent) lors de la calcination à un (des) oxyde (s) collant (s) pourra-t-il (pourront-ils) être le nitrate de sodium, l'acide phosphomolybdique ou encore le nitrate de bore ou des mélanges de ceux-ci.Thus, the compound (s) such as the nitrate (s) and / or the other compound (s) which conduct (conduct) during calcination to an oxide (s) whether sticky (s) could they be sodium nitrate, phosphomolybdic acid or boron nitrate or mixtures thereof.
La teneur en ce ou ces composé (s) tel (s) que le ou les nitrate (s) « collant (s) » et/ou autres composés « collants » dans l'effluent, exprimée en oxydes, par rapport à la masse totale de nitrates contenus dans l'effluent, exprimée aussi en oxydes, est généralement supérieure à 35% en masse, ou supérieure à 30% en masse pour le nitrate de sodium exprimé en oxydes .The content of this or these compound (s) such as the "sticky" nitrate (s) and / or other "sticky" compounds in the effluent, expressed in oxides, relative to the mass total of nitrates contained in the effluent, also expressed in oxides, is generally greater than 35% by weight, or greater than 30% by weight for the sodium nitrate expressed in oxides.
Au lieu de la masse totale de nitrates contenus dans l'effluent, exprimée en oxydes, on pourrait éventuellement, plus précisément, utiliser la masse totale de sels (y compris les nitrates) contenus dans l'effluent, exprimée en oxydes. Le procédé selon l'invention permet en particulier la calcination d'effluents présentant une teneur élevée en composés tels que nitrates et autres composés dits « collants », à savoir supérieure à 35% en masse pour l'ensemble des nitrates « collants », ou supérieure à 30% en masse, pour le nitrate de sodium.Instead of the total mass of nitrates contained in the effluent, expressed in oxides, one could possibly, more precisely, use the total mass of salts (including nitrates) contained in the effluent, expressed in oxides. The process according to the invention makes it possible in particular to calcinate effluents with a high content of compounds such as nitrates and other so-called "sticky" compounds, ie greater than 35% by weight for all of the "sticky" nitrates, or greater than 30% by weight, for sodium nitrate.
De manière particulièrement avantageuse, le procédé selon l'invention permet la calcination de solutions à forte teneur en sodium qui sont très collantes.Particularly advantageously, the process according to the invention allows the calcination of high sodium solutions which are very tacky.
Par « forte teneur » en sodium, plus précisément en nitrate de sodium, on entend généralement que l'effluent a une teneur en nitrate de sodium, exprimée en oxyde de sodium, par rapport à la masse totale des nitrates (ou éventuellement, plus précisément, par rapport à la masse totale des sels) contenus dans l'effluent, exprimée en oxydes supérieure à 30% en masse, de préférence supérieure à 50% en masse . Les inéquations mentionnées ci-dessus étant respectées, dans le mélange formé après addition de l'adjuvant de dilution dans l'effluent à calciner, et les problèmes de colmatage étant de ce fait évités, un seul essai de calcination permet d'optimiser les caractéristiques du calcinât en jouant sur la chauffe des différentes zones du calcinateur, sur la teneur en adjuvant de calcination (généralement) et la vitesse de rotation du tube du calcinateur.By "high content" in sodium, more specifically in sodium nitrate, it is generally understood that the effluent has a sodium nitrate content, expressed as sodium oxide, relative to the total mass of the nitrates (or possibly, more precisely , relative to the total mass of salts) contained in the effluent, expressed in oxides of greater than 30% by weight, preferably greater than 50% by weight. The inequalities mentioned above being respected, in the mixture formed after addition of the dilution adjuvant in the effluent to be calcined, and clogging problems being thereby avoided, a single calcination test makes it possible to optimize the characteristics. calcinates by varying the heating of the different calciner zones, the calcination aid content (generally) and the rotational speed of the calciner tube.
Les conditions de cette calcination, mis à part le fait notable que tout colmatage est évité, ne sont pas fondamentalement modifiées par le fait que l'addition d'adjuvant de dilution doit satisfaire aux critères ajoutés par les inéquations (1) et (2) .The conditions of this calcination, apart from the notable fact that any clogging is avoided, are not fundamentally altered by the fact that the addition of dilution adjuvant must meet the criteria added by inequations (1) and (2).
Les conditions de la calcination sont généralement les suivantes : température atteinte par le calcinât d'environ 4000C.The conditions for calcination are generally as follows: temperature reached by the calcine of about 400 0 C.
Cette étape de calcination est généralement réalisée dans un tube tournant chauffé, de préférence jusqu'à la température voulue indiquée ci-dessus par exemple par un four électrique à plusieurs zones de chauffe indépendantes.This calcination step is generally carried out in a heated rotating tube, preferably up to the desired temperature indicated above, for example by an electric furnace with several independent heating zones.
Des zones de chauffe sont plus particulièrement dédiées à l' évaporation et d'autres à la calcination. Les zones de calcination permettent de chauffer le calcinât à la température de 4000C. En d'autres termes, l'étape de calcination est réalisée à une température de calcinât en sortie de four d'environ 400°C.Heating zones are more particularly dedicated to evaporation and others to calcination. The calcination zones make it possible to heat the calcine at the temperature of 400 ° C. In other words, the calcination step is carried out at a furnace calcine temperature of about 400 ° C.
La vitesse de rotation du tube, l'ajout de l'adjuvant de calcination et la présence d'une barre folle permettent de diviser le calcinât solide pour que celui-ci puisse réagir dans de bonnes conditions dans l'unité de vitrification.The speed of rotation of the tube, the addition of the calcination aid and the presence of an idle bar makes it possible to divide the solid calcine so that it can react under good conditions in the vitrification unit.
Le procédé de traitement selon l'invention comprend généralement, après l'étape de calcination, une étape de vitrification du calcinât obtenu lors de cette étape de calcination. Cette étape de vitrification consiste en une réaction entre le calcinât et une fritte de verre (verre préformé) pour obtenir un verre de confinement. En d'autres termes, après l'étape de calcination, on effectue une étape de vitrification qui consiste à élaborer un verre de confinement à partir de la fusion du calcinât issu de l'étape de calcination avec de la fritte de verre.The treatment process according to the invention generally comprises, after the calcination step, a vitrification step of the calcine obtained during this calcination step. This vitrification step consists of a reaction between the calcine and a glass frit (preformed glass) to obtain a confinement glass. In other words, after the calcination step, a vitrification step is performed which consists in developing a confinement glass from the melting of the calcine from the calcination step with glass frit.
Comme on l'a déjà précisé plus haut, la mise en œuvre de préférence dans l'adjuvant de dilution des nitrates spécifiques de fer et de terres rares permet en outre de manière avantageuse d'assouplir les contraintes quant à la formulation du verre. En particulier, on peut incorporer une proportion supérieure d'effluent dans le verre lorsque le calcinât a été obtenu en utilisant l'adjuvant de dilution selon l'invention en lieu et place d'un adjuvant de dilution constitué uniquement de nitrate d'aluminium.As already mentioned above, the implementation preferably in the dilution adjuvant of iron and rare earth-specific nitrates also advantageously makes it possible to relax the constraints with regard to the formulation of the glass. In particular, a higher proportion of effluent in the glass can be incorporated when the calcine was obtained using the dilution adjuvant according to the invention in place of a dilution adjuvant consisting solely of aluminum nitrate.
En d'autres termes, la borne contraignante sur le taux d'incorporation d'effluents dans le verre, due au nitrate d'aluminium, se trouve supprimée, et le taux d' incorporation est nettement accru et passe par exemple de 13% en masse d'oxydes à 18% en masse d'oxydes par rapport à la masse totale du verre. En outre, l'apport important d'aluminium dans le cas d'un adjuvant de dilution constitué uniquement de nitrate d' aluminium a tendance à faire durcir le calcinât et a pour conséquence de provoquer une baisse de la réactivité entre le calcinât et la fritte de verre dans le four de vitrification.In other words, the limit binding on the rate of incorporation of effluents into the glass, due to aluminum nitrate, is suppressed, and the incorporation rate is significantly increased and passes for example 13% in oxide mass at 18% by weight of oxides relative to the total mass of the glass. In addition, the high intake of aluminum in the case of a dilution admixture consisting solely of aluminum nitrate tends to harden the calcine and has the consequence of causing a decrease in the reactivity between the calcine and the frit of glass in the vitrification furnace.
Au contraire, l'ajout de fer rend le calcinât plus friable et donc plus facile à vitrifier.On the contrary, the addition of iron makes the calcine more friable and therefore easier to vitrify.
La vitrification consiste en une réaction de fusion entre le calcinât et la fritte de verre pour former un verre de confinement. Elle est réalisée dans deux types de fours : les fours à induction indirecte qui consistent à chauffer par quatre inducteurs un pot métallique dans lequel est introduit le mélange fritte/calcinat, et les fours à induction directe qui consistent à chauffer le verre par un inducteur à travers une structure refroidie (creuset froid) qui laisse passer une partie du champ électromagnétique et dans laquelle est introduit en continu le mélange fritte/calcinat.Vitrification consists of a melting reaction between the calcine and the glass frit to form a confining glass. It is made in two types of ovens: indirect induction ovens which consists of heating by four inductors a metal pot into which the sintered / calcined mixture is introduced, and the direct induction furnaces which consist in heating the glass by an inductor through a cooled structure (cold crucible) which allows part of the electromagnetic field and in which is introduced continuously the sintered mixture / calcinate.
L'invention va maintenant être décrite en référence aux exemples suivants, donnés à titre illustratif et non limitatif.The invention will now be described with reference to the following examples, given by way of illustration and not limitation.
Exemple 1 : Dans cet exemple, on décrit la calcination d'un effluent contenant une forte teneur en nitrate de sodium.Example 1: In this example, the calcination of an effluent containing a high content of sodium nitrate is described.
La composition de cet effluent (déchet) est donnée dans le tableau 1, cette composition étant exprimée en % massique des oxydes correspondant aux sels contenus dans l' effluent, qui sont des nitrates.The composition of this effluent (waste) is given in Table 1, this composition being expressed in% by weight of the oxides corresponding to the salts contained in the effluent, which are nitrates.
Le pourcentage des oxydes est exprimé par rapport à la masse totale des oxydes correspondant aux sels contenus dans l' effluent . L' effluent décrit dans le tableau 1 ci- dessous est très chargé notamment en sodium et par conséquent très collant.The percentage of oxides is expressed in relation to the total mass of the oxides corresponding to the salts contained in the effluent. The effluent described in Table 1 below is very charged especially in sodium and therefore very sticky.
Selon l'invention dans la solution de mélange de l' effluent (du déchet) avec l'adjuvant de dilution (quel qu'il soit) les deux inéquations suivantes doivent être vérifiées , - , masse de nitrate de sodium du mélange exprimée en termes d'oxyde Na2OAccording to the invention in the solution of mixing the effluent (of the waste) with the dilution adjuvant (whatever it is) the two following inequations must be verified - mass of sodium nitrate of the mixture expressed in terms of oxide Na 2 O
( I j < 0,3 masse de tous les composés du mélange tels que des nitrates exprimée en termes d'oxydes(I j <0.3 mass of all compounds in the mixture, such as nitrates expressed in terms of oxides
masse de tous les composés du mélange tels que des nitrates conduisant lors de leur calcination à . „ . des oxydes collants exprimée en termes d'oxydes masse de tous les composés du mélange exprimée en termes d'oxydesmass of all compounds in the mixture such as nitrates leading to calcination at. " sticky oxides expressed in terms of the mass oxides of all the compounds of the mixture expressed in terms of oxides
ou plus simplementor more simply
masse de Na2O < Q 3 masse de tous les oxydes du mélangemass of Na 2 O <Q 3 mass of all the oxides of the mixture
masse des oxydes collants masse de tous les oxydes du mélangemass of sticky oxides mass of all the oxides of the mixture
L'application du critère de calcination à l'effluent particulier décrit dans le Tableau 1 s'exprime par :The application of the calcination criterion to the particular effluent described in Table 1 is expressed by:
masse de Na2O ≤ Q ^ ( i ) masse de tous les oxydes du mélangemass of Na 2 O ≤ Q ^ (i) mass of all the oxides of the mixture
etand
somme des masses de NaO2 , de MoO3 et de B2O3 masse de tous les oxydes du mélangesum of masses of NaO 2 , MoO 3 and B 2 O 3 mass of all the oxides of the mixture
En effet, l'homme du métier identifie facilement les oxydes collants (ou plus précisément les oxydes collants qui sont générés par la calcination des nitrates ou des autres composés se trouvant dans l'effluent) de cet effluent qui sont Na2O, MoO3 et B2O3.Indeed, those skilled in the art easily identify the sticky oxides (or more precisely the sticky oxides which are generated by the calcination of the nitrates or other compounds in the effluent) of this effluent which are Na 2 O, MoO 3 and B 2 O 3 .
Pour cet effluent, c'est la seconde inéquation qui est la plus contraignante. Si l'on se place à la limite du domaine défini par l'inéquation (2), la proportion d' effluent liquide (solution) exprimée en oxydes, dans le mélange effluent liquide sera au maximum de 51,27% en masse et ce quel que soit l'adjuvant utilisé. En effet, l'inéquation (2) donne pour cet effluent :For this effluent, it is the second inequation that is the most restrictive. If we consider the limit of the area defined by the inequation (2), the proportion of liquid effluent (solution) expressed in oxides, in the liquid effluent mixture will be at most 51,27% by mass and this whatever adjuvant is used. Indeed, the inequation (2) gives for this effluent:
56,43 + 5,71 + 6,1356.43 + 5.71 + 6.13
<0,35 100 + x<0.35 100 + x
x représentant la masse d'adjuvant de dilution ajoutée exprimée en oxyde soit :x representing the added dilution adjuvant mass expressed as oxide, namely:
68,27 < 35 + 0,35x, et donc x > 95,0568.27 <35 + 0.35x, and thus x> 95.05
II s'ensuit que la proportion maximale d' effluent liquide (solution) dans le mélange sera donc de :It follows that the maximum proportion of liquid effluent (solution) in the mixture will therefore be:
100100
= 0,5127= 0.5127
95,05 + 100 soit 51,27%.95.05 + 100 or 51.27%.
En conséquence, eu égard aux calculs ci- dessus, on ajoute à l'effluent du Tableau 1 un adjuvant (adjuvant 1) qui est constitué de 100% en masse de nitrate d'aluminium exprimé en oxyde Al2O3, à raison de 95,05% en masse d'adjuvant exprimé en oxyde pour 100% en masse d'effluent exprimé en % en masse des oxydes correspondant aux sels contenus dans l'effluent. Il est à noter que la quantité d'adjuvant a été minimisée grâce à l'application des critères selon l'invention. Les conditions de la calcination sont les suivantes :Consequently, in view of the above calculations, an adjuvant (adjuvant 1) is added to the effluent of Table 1 which consists of 100% by weight of aluminum nitrate, expressed as Al 2 O 3 oxide, at the rate of 95.05% by weight of adjuvant expressed as oxide for 100% in mass of effluent expressed in% by weight of the oxides corresponding to the salts contained in the effluent. It should be noted that the amount of adjuvant has been minimized by applying the criteria according to the invention. The conditions of calcination are as follows:
Calcinateur à quatre zones de chauffe indépendantes, la température atteinte par le calcinât est d'environ 4000C, la vitesse de rotation du tube tournant contenant la barre folle est de 20 tr/mn, la teneur en adjuvant de calcination est de 40 g/L du mélange de l'effluent avec l'adjuvant de dilution.Calcinator with four independent heating zones, the temperature reached by the calcine is about 400 ° C., the speed of rotation of the rotating tube containing the idler bar is 20 rpm, the calcination aid content is 40 g / L of the effluent mixture with the dilution adjuvant.
On n'observe aucun collage sur les parois et aucun colmatage du calcinateur.There is no sticking on the walls and no clogging of the calciner.
Exemple 2 :Example 2
Dans cet exemple, on réalise la calcination du même effluent que celui de l'exemple 1 et décrit dans le tableau 1. On ajoute à cet effluent un adjuvantIn this example, the calcination of the same effluent as that of Example 1 and described in Table 1 is carried out. An adjuvant is added to this effluent.
(adjuvant 2) préféré selon l'invention qui est constitué de 75% en masse de nitrate d'aluminium exprimé en oxyde AI2O3 et de 25% en masse de nitrate de fer exprimé en oxyde Fe2Û3. Cet adjuvant est ajouté dans une même quantité que l'adjuvant 1 déterminée par les mêmes calculs sur la base des critères selon 1' invention .(Adjuvant 2) preferred according to the invention which consists of 75% by weight of aluminum nitrate expressed as Al 2 O 3 oxide and 25% by weight of iron nitrate expressed as Fe 2 O 3 oxide. This adjuvant is added in the same amount as the adjuvant 1 determined by the same calculations on the basis of the criteria according to the invention.
On ajoute ainsi 95,05% en masse d'adjuvant exprimé en oxydes pour 100% en masse d'effluent (déchet) exprimé en % en masse des oxydes correspondant aux sels contenus dans l'effluent. Les conditions de la calcination sont les mêmes que celle de l'exemple 1.95.05% by weight of adjuvant, expressed in oxides, is thus added per 100% by mass of effluent (waste) expressed in% by weight of the oxides corresponding to the salts contained in the effluent. The conditions of the calcination are the same as that of Example 1.
On n'observe aucun collage sur les parois et aucun colmatage du calcinateur.There is no sticking on the walls and no clogging of the calciner.
TABLEAU 1TABLE 1
Exemple 3 :Example 3
Dans cet exemple, on procède à la vitrification du calcinât obtenu dans l'exemple 1.In this example, the vitrification of the calcine obtained in Example 1 is carried out.
Rappelons que ce calcinât a été préparé en utilisant un adjuvant (« adjuvant n°l ») constitué uniquement de nitrate d'aluminium. Le domaine de composition du verre que nous étions en mesure d'élaborer impose une teneur maximale en alumine de 13% en masse dans le verre.Recall that this calcine was prepared using an adjuvant ("adjuvant No. 1") consisting solely of aluminum nitrate. The range of glass composition that we were able to develop requires a maximum alumina content of 13% by weight in the glass.
Le verre est élaboré à partir du calcinât et d'une fritte de verre contenant 1 % en masse d'alumine. La vitrification a été réalisée en creuset froid à 12300C.The glass is made from calcine and a glass frit containing 1% by weight of alumina. The vitrification was carried out in a cold crucible at 1230 ° C.
Exemple 4 : Dans cet exemple, on procède à la vitrification du calcinât obtenu dans l'exemple 2. Rappelons que ce calcinât a été préparé en utilisant un adjuvant préféré (« adjuvant n°2 ») constitué de 75% en masse de sel d'aluminium et de 25% en masse de sel de fer.Example 4: In this example, the vitrification of the calcine obtained in Example 2 is carried out. It should be remembered that this calcine was prepared using a preferred adjuvant ("adjuvant # 2") consisting of 75% by weight of sodium salt. aluminum and 25% by weight of iron salt.
Il a été déterminé que le taux d' incorporation maximum du déchet initial (donc avant mélange) est limité à 12,9% en masse du verre dans l'exemple 3 alors que dans le présent exemple 4, le taux d'incorporation maximum est de 17,3%.It was determined that the maximum incorporation rate of the initial waste (thus before mixing) is limited to 12.9% by weight of the glass in Example 3 whereas in the present Example 4, the maximum incorporation rate is 17.3%.
De plus, l'apport important d'aluminium par l'adjuvant n°l a tendance à faire durcir le calcinât et a pour conséquence de provoquer une légère baisse de réactivité entre le calcinât et la fritte de verre dans le four de vitrification.In addition, the high intake of aluminum by the adjuvant No. 1 tends to harden the calcine and results in a slight decrease in reactivity between the calcine and the glass frit in the vitrification furnace.
Au contraire, l'apport de fer avec l'adjuvant n°2, selon l'invention, rend le calcinât plus friable et donc plus facile à vitrifier. Exemple 5 :On the contrary, the addition of iron with adjuvant No. 2, according to the invention, makes the calcine more friable and therefore easier to vitrify. Example 5
Dans cet exemple, on décrit la calcination d'un effluent constitué à 100% de nitrate de sodium décrit dans le tableau 2.In this example, the calcination of an effluent consisting of 100% sodium nitrate described in Table 2 is described.
Selon une première manipulation, on ajoute à cet effluent un adjuvant (adjuvant 1) de l'art antérieur qui est constitué de 100% en masse de nitrate d'aluminium exprimé en oxyde AI2O3. Selon une seconde manipulation, la calcination du nitrate de sodium est réalisée avec un adjuvant (adjuvant 3) selon l'invention dans lequel une partie du nitrate d'aluminium est remplacée par des nitrates de lanthane, de cérium, de néodyme et de praséodyme.According to a first manipulation, there is added to this effluent a builder (adjuvant 1) of the prior art which consists of 100% by weight of aluminum nitrate expressed as Al 2 O 3 oxide. According to a second manipulation, the calcination of sodium nitrate is carried out with an adjuvant (adjuvant 3) according to the invention in which part of the aluminum nitrate is replaced by nitrates of lanthanum, cerium, neodymium and praseodymium.
Pour les deux cas, la teneur en adjuvant de dilution est donnée par l'inéquation (1) qui conduit à :In both cases, the dilution adjuvant content is given by the inequation (1) which leads to:
100 + x x représentant la masse d'adjuvant de dilution ajoutée exprimée en oxyde soit :100 + x x representing the added dilution adjuvant mass expressed in oxide, namely:
100 < 30 + 0,3x, et donc x > 233,33100 <30 + 0.3x, and thus x> 233.33
La teneur minimale d'adjuvant de dilution à ajouter à cet effluent constitué uniquement de nitrate de sodium exprimée en masse d'oxyde totale représente 70% dans le mélange de l' effluent avec l'adjuvant de dilution . Les conditions de la calcination sont les suivantes : Calcinateur à deux zones de chauffe indépendantes, la température atteinte par le calcinât est d'environ 4000C, la vitesse de rotation du tube tournant contenant la barre folle est de 35 tr/mn, la teneur en adjuvant de calcination est de 20 g/L du mélange de l'effluent avec l'adjuvant de dilution.The minimum content of dilution adjuvant to be added to this effluent consisting solely of sodium nitrate expressed as total oxide mass represents 70% in the mixture of the effluent with the dilution adjuvant. The conditions of calcination are as follows: Calcinator with two independent heating zones, the temperature reached by the calcine is approximately 400 ° C., the speed of rotation of the rotating tube containing the idler bar is 35 rpm, the calcination aid content is 20 g / L of the effluent mixture with the dilution adjuvant.
TABLEAU 2TABLE 2

Claims

REVENDICATIONS
1. Procédé de traitement d'un effluent liquide aqueux nitrique contenant des nitrates de métaux ou de métalloïdes, comprenant une étape de calcination de l' effluent pour transformer les nitrates de métaux ou de métalloïdes en oxydes des métaux ou métalloïdes, au moins un composé choisi les nitrates de métaux ou de métalloïdes et les autres composés de 1' effluent conduisant lors de la calcination à un oxyde collant, et un adjuvant de dilution comprenant au moins un nitrate de métal ou de métalloïde conduisant lors de la calcination à un oxyde non collant étant ajouté à 1' effluent préalablement à l'étape de calcination pour donner un mélange d' effluent et d'adjuvant de dilution, dans lequel le mélange vérifie les deux inéquations suivantes (1) (2) :A method of treating an aqueous nitrate liquid effluent containing nitrates of metals or metalloids, comprising a step of calcining the effluent to transform the nitrates of metals or metalloids into oxides of metals or metalloids, at least one compound selected nitrates of metals or metalloids and other compounds of the effluent resulting in the calcination of a sticky oxide, and a dilution adjuvant comprising at least one nitrate of metal or metalloid leading to the calcination of a non-oxide sticking agent being added to the effluent prior to the calcination step to give a mixture of effluent and dilution adjuvant, wherein the mixture satisfies the following two inequations (1) (2):
masse de nitrate de sodium du mélange exprimée en termes d'oxyde Na2O masse de tous les composés du mélange exprimée en termes d'oxydesmass of sodium nitrate of the mixture expressed in terms of oxide Na 2 O mass of all the compounds of the mixture expressed in terms of oxides
masse de tous les composés du mélange conduisant lors de leur calcination à des oxydes collants, exprimée en termes d'oxydes masse de tous les composés du mélange exprimée en termes d'oxydesmass of all the compounds of the mixture leading, when calcined, to sticky oxides, expressed in terms of the mass oxides of all the compounds of the mixture, expressed in terms of oxides
2. Procédé selon la revendication 1, dans lequel l'adjuvant de dilution comprend du nitrate d'aluminium et éventuellement au moins un autre nitrate choisi parmi le nitrate de fer et les nitrates de terres rares. 2. The method of claim 1, wherein the dilution adjuvant comprises aluminum nitrate and optionally at least one other nitrate selected from iron nitrate and rare earth nitrates.
3. Procédé selon la revendication 2, dans lequel l'adjuvant de dilution comprend du nitrate d'aluminium et éventuellement au moins un autre nitrate choisi parmi le nitrate de fer, le nitrate de lanthane, le nitrate de cérium, le nitrate de praséodyme et le nitrate de néodyme.The process according to claim 2, wherein the dilution adjuvant comprises aluminum nitrate and optionally at least one other nitrate selected from iron nitrate, lanthanum nitrate, cerium nitrate, praseodymium nitrate and neodymium nitrate.
4. Procédé selon l'une quelconque des revendications précédentes, dans lequel le au moins un composé conduisant lors de la calcination à un (des) oxyde (s) collant (s) est (sont) choisi (s) parmi le nitrate de sodium, l'acide phosphomolybdique, le nitrate de bore et leurs mélanges.4. Method according to any one of the preceding claims, wherein the at least one compound leading on calcination to a tacky oxide (s) is (are) chosen from sodium nitrate , phosphomolybdic acid, boron nitrate and mixtures thereof.
5. Procédé selon l'une quelconque des revendications précédentes, dans lequel la teneur en nitrate (s) et autre (s) composé (s) conduisant lors de la calcination à un oxyde collant, exprimée en oxyde, par rapport à la masse totale des sels contenus dans l'effluent, exprimée en oxyde, est supérieure à 35% en masse .5. Method according to any one of the preceding claims, wherein the content of nitrate (s) and other (s) compound (s) leading during the calcination to a tacky oxide, expressed as oxide, relative to the total mass salts contained in the effluent, expressed as oxide, is greater than 35% by weight.
6. Procédé selon la revendication 5, dans lequel l'effluent a une teneur en nitrate de sodium, exprimée en oxyde de sodium Na2<0, par rapport la masse totale des sels contenus dans l'effluent, exprimée en oxyde, supérieure à 30% en masse.6. Process according to claim 5, in which the effluent has a sodium nitrate content, expressed as sodium oxide Na2 <0, relative to the total mass of the salts contained in the effluent, expressed as oxide, greater than 30. % by mass.
7. Procédé selon l'une quelconque des revendications précédentes, dans lequel l'étape de calcination est réalisée à une température conduisant à une température de calcinât en sortie de four d'environ 4000C.7. A process according to any one of the preceding claims, wherein the calcination step is carried out at a temperature leading to a calcine temperature at the oven outlet of approximately 400 ° C.
8. Procédé selon l'une quelconque des revendications précédentes, dans lequel la calcination est réalisée dans un tube tournant chauffé.8. A process according to any one of the preceding claims, wherein the calcination is carried out in a heated rotating tube.
9. Procédé selon l'une quelconque des revendications précédentes, dans lequel après l'étape de calcination on effectue une étape de vitrification qui consiste à élaborer un verre de confinement à partir de la fusion du calcinât issu de l'étape de calcination avec de la fritte de verre. 9. Method according to any one of the preceding claims, wherein after the calcination step is carried out a vitrification step which consists in developing a confinement glass from the melting of the calcine from the calcination step with the glass frit.
EP09799361A 2008-12-30 2009-12-23 Method for processing a nitrous aqueous liquid effluent by calcination and vitrification Active EP2374135B1 (en)

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