WO2001092152A1 - Method for recuperating a metal in carbonate or hydrogenocarbonate form - Google Patents

Method for recuperating a metal in carbonate or hydrogenocarbonate form Download PDF

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Publication number
WO2001092152A1
WO2001092152A1 PCT/FR2001/001675 FR0101675W WO0192152A1 WO 2001092152 A1 WO2001092152 A1 WO 2001092152A1 FR 0101675 W FR0101675 W FR 0101675W WO 0192152 A1 WO0192152 A1 WO 0192152A1
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Prior art keywords
metal
carbonate
hydroxide
injection
effluent
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PCT/FR2001/001675
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French (fr)
Inventor
Philippe Guillaume
Original Assignee
Carboxyque Francaise
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Publication date
Application filed by Carboxyque Francaise filed Critical Carboxyque Francaise
Priority to AU2001274154A priority Critical patent/AU2001274154A1/en
Publication of WO2001092152A1 publication Critical patent/WO2001092152A1/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C01F11/181—Preparation of calcium carbonate by carbonation of aqueous solutions and characterised by control of the carbonation conditions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G11/00—Compounds of cadmium
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62—Heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62—Heavy metal compounds
    • C02F1/64—Heavy metal compounds of iron or manganese
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the present invention relates to a new process for recovering a metal in the form of carbonate or hydrogen carbonate.
  • the present invention provides a particularly simple and effective means for recovering with the desired selectivity and yield a metal in an aqueous medium.
  • the invention applies to all environments in which the metal is initially found in the form of hydroxide or is capable of transforming into hydroxide in particular by the action of a strong base.
  • the invention consists in transforming the metal into hydroxide when it is not in this form initially in the medium to be treated and in bringing, if necessary, the pH of the medium to a value defined to transform ⁇ iydroxide into carbonate by injection of CO 2 , said injection being carried out under controlled conditions where this carbonate or this hydrogenocarbonate is brought to its minimum solubility in the medium.
  • the invention is mainly based on the fact that the solubility of metals varies with the pH and the nature of the ions present in the medium (effect of common ions) and is based on the fact that it is possible to predetermine the pH value to which the medium must be brought so that the hydrogen carbonate or the carbonate formed by injection of CO 2 is at its minimum of solubility, thus making it possible to precipitate the metal as best as possible in the form of carbonate or hydrogen carbonate.
  • the invention relates to a process for treating an aqueous medium containing a metal in the form of hydroxide or capable of transforming into hydroxide by the introduction of a base into said medium, said treatment being intended to recover said metal in the form of carbonate or hydrogen carbonate, characterized in that it comprises a step of injecting carbon dioxide in an amount sufficient to bring the pH of said medium to a predetermined value.
  • the predetermined value of the final precipitation pH of the carbonate or metal hydrogen carbonate is determined experimentally and / or from the knowledge of a person skilled in the art concerning the solubility of the carbonate or the hydrogen carbonate of the metal which it is sought to recover in function of the pH and is advantageously determined to obtain the rr ⁇ iimum solubility of the carbonate or hydrogen carbonate of said metal in said medium.
  • the determination of the pH where the carbonate or hydrogen carbonate is at least of its solubility in the medium concerned can be done by injection into a medium containing the corresponding hydroxide, carbon dioxide by monitoring the pH so as to obtain at the end of injection the pH value corresponding to this desired minimum solubility.
  • the introduction of a base into the medium to be treated prior to the introduction of carbon dioxide is only done to ensure that both we are initially at a pH higher than the predetermined pH value allowing the desired optimal precipitation of the carbonate or of the hydrogen carbonate and that the metal is present before its transformation by CO 2 in the form of a hydroxide.
  • the skilled person uses his fundamental knowledge concerning the acidic or basic character of the metal hydroxide of the metal which he seeks to recover. It takes into account in particular that the essential factor determining the acidic or basic character of a hydroxide is the polarizing power of the metallic atom which depends on the size of the atom and its degree of oxidation.
  • This alkaline treatment consists in increasing the pH of the medium to be treated, for example with potash, soda or any other strong base allowing the pH to be brought to a value higher than the predetermined value of precipitation of the metal in the form of carbonate. or hydrogen carbonate and transforming the metal initially into solution in the form of hydroxide.
  • the CO 2 is then introduced into the medium to be treated, so as to cause precipitation by a common ion effect, depending on the metal to be treated, either of its carbonate or of its hydrogenocarbonate.
  • the introduction of CO 2 is carried out under conditions such that the final pH of the medium corresponds to a predetermined value, this value making it possible to precipitate the carbonate or the hydrogen carbonate with the selectivity and / or the desired recovery yield.
  • this value is chosen so that the precipitation is as complete as possible, that is to say that the solubility of this carbonate or this hydrogenocarbonate is minimal in the medium.
  • carbon dioxide is in all cases injected into a medium which is at a pH higher than that of the predetermined value to which it is desired to bring the pH by introduction of this CO 2 .
  • the effect of this base is both to modify the pH before the injection of carbon dioxide but also, if necessary, to transform the metal into hydroxide.
  • CO 2 injection is carried out as long as the pH setpoint is not reached. This introduction is stopped as soon as the setpoint is reached.
  • a sample of the liquid to be treated is taken, on which an analysis is carried out making it possible to quantify the concentration of dissolved metal in the liquid, and this in order to ensure that we are at an acceptable residual metal concentration.
  • the invention is applicable to all metals capable of being precipitated in the form of carbonate or hydrogen carbonate from their hydroxide by the introduction of CO 2 into an alkaline medium containing them. It applies very particularly to alkali metals and, in particular, to Hthium, to alkaline earth metals and, in particular, to calcium, to strontium, to magnesium and to barium. It also applies to zinc, manganese, cadmium, copper and lead.
  • a person skilled in the art is capable of determining the optimal conditions for precipitation of the target form of this metal and of supplementing them by experimental tests to fix the pH serving as a reference value during the injection of CO 2 .
  • Carbon dioxide can be injected either in gaseous form or in liquid form.
  • This injection can be done either directly in the aqueous medium to be treated, or indirectly in a recirculation loop provided for this purpose.
  • the carbon dioxide is transformed into carbonic acid which is a weak diacid presenting a neutralization curve with a gentle slope.
  • the medium to be treated is, if necessary, subjected to agitation during the treatment with CO 2 . This agitation is then either stopped to ensure a better precipitation of the carbonate or hydrogen carbonate formed is maintained if one seeks to keep the precipitate in suspension for the duration of the treatment.
  • CO 2 makes it possible to avoid any secondary saline pollution.
  • the invention is very particularly applicable to the treatment of various industrial effluents, with a view to ridding them of the metals contained with concern, respect for environmental standards and / or the recovery of these metals with a view to their subsequent recovery.
  • the invention also applies to the recycling treatment of metals used in the battery and accumulator industry, in particular manganese, zinc, hthium, cadmium, lead and copper.
  • these aqueous mediums are first of all treated, if necessary, with a strong base so as to be placed at a pH higher than the set value imposed during the injection of CO 2 and in which the metal is at least partially in the form of hydroxide.
  • the regulation of the pH by carbon dioxide is then done, as the case may be, either in a neutralization tank, in particular in the case of the treatment of an effluent, or in a reactor, in particular in the case of the treatment of an alkaline solution from the battery and accumulator industry.
  • the pH set point is determined which corresponds to the final pH to be reached during the injection of carbon dioxide so as to have the minimum desired residual concentration of recovered metal.
  • This setpoint corresponds to the maximum precipitation of the metal in the form of carbonate or hydrogen carbonate and therefore at the minimum value of the content of dissolved metal in the medium.
  • the CO 2 is then injected either in gaseous form or in liquid form into the medium by slaving the injection to the measurement of the pH in the liquid to be treated.
  • Figures 1 and 2 attached illustrate two embodiments of the process of the invention, respectively in the case where the neutralization is done in a tank ( Figure 1) and where the process is carried out in a stirred reactor ( Figure 2).
  • an effluent to be treated is introduced through the pipe 2 into the tank 1 provided with a device 4 for mechanical agitation.
  • a recirculation circuit 5 provided with a pump 6 ensures recirculation of the effluent.
  • This circuit comprises a tubular reactor 7 fitted with a device for injecting carbon dioxide via an injection solenoid valve 8.
  • the pH of the medium to be treated is continuously measured by a pH meter 9.
  • a control cabinet fitted with an electrical supply, allows the opening of valve 8 to be subject to the pH measurement carried out by pH meter 9 so as to close the CO 2 injection valve when the set value pH is reached.
  • the CO 2 injection is carried out by recirculation of part of the effluent to be treated.
  • This injection can be carried out either in the form of liquid CO 2 or in the form of gaseous CO 2 by conventional devices for injecting CO 2 into a circuit.
  • FIG. 2 shows an embodiment of the invention in which the solution to be treated is placed in a stirred reactor. We use such reactor, in particular for treating alkaline solutions from the treatment of alkaline batteries and accumulators and containing, in solution, the metal to be recovered.
  • the alkaline solution containing the metal to be recovered is introduced into a reactor 11 provided with a pH meter 9.
  • the solution to be treated is recirculated by l '' through a recirculation circuit 5 comprising a
  • Liquid CO 2 is introduced into the tubular reactor by means of the solenoid valve 8, the opening of which is controlled as in the previous case by means of a regulation device contained in a regulation cabinet 10.
  • the injection of CO 2 can also be carried out according to the same scheme using CO 2 gas. It is also possible to envisage introducing gaseous CO 2 directly into this reactor, using an injection turbine or porous candles, into a stirred reactor such as that shown in FIG. 2.
  • Industrial waste water containing strontium in the form of hydroxide at an initial pH of 12.4 is treated in a device as shown in FIG. 1.
  • the strontium content of the effluent to be treated is 6400 ppm.
  • the effluent is collected in a stirred tank as shown in FIG. 1.
  • the CO 2 is injected in liquid or gaseous form by recirculating part of the effluent to be treated.
  • the aim is to bring the strontium content to a value of less than 1 ppm so as to comply with the standard in force concerning the authorized contents of this metal in an effluent.
  • the treatment is carried out at atmospheric pressure and at ambient temperature.
  • the pH setpoint is fixed at 9 so as to obtain maximum precipitation of the strontium carbonate and to reach a minimum dissolved strontium value of 0.6 ppm.
  • a measurement of the residual metal concentration after treatment with CO 2 is carried out by a flame emission technique.
  • the batteries are first crushed, the active materials are then separated from the metal housings by mechanical screening.
  • the active materials are then dissolved in an alkaline medium. These are alkaline solutions of this type which are treated in Examples 2a and 2b below.
  • the final pH setpoint to be reached during the CO 2 injection is 8, so as to obtain zinc hydrogen carbonate.
  • a solution from a treatment of cell waste in a stirred reactor is treated.
  • the treated solution is initially at an acidic pH of between 4 and 5.
  • sodium hydroxide is injected so as to gradually transform the manganese into manganese hydroxide, then CO 2 is injected by displaying a pH setpoint. 8.5.
  • the process is carried out, at ambient temperature and under atmospheric pressure, in a stirred reactor of the type shown in FIG. 2.
  • the sodium hydroxide is introduced in this example into the tubular reactor 7 upstream of the point CO 2 introduction.
  • a static mixer in hgne (not shown in FIG. 2) makes it possible to improve the contact. All of these conditions make it possible to make the transformation into carbonate almost instantaneous as soon as the hydroxide is formed and to avoid the drawbacks which would result from the precipitation of the hydroxide in the medium.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
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  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
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Abstract

The invention concerns a method for treating an aqueous medium containing a metal in hydroxyl form or capable of being transformed into hydroxide by introducing a base in said medium, said treatment being designed to recuperate said metal in carbonate or hydrogenocarbonate form. The invention is characterised in that it comprises a step which consists in injecting carbon dioxide in sufficient amount to bring the pH of said medium to a predetermined value corresponding to the minimum solubility of carbonate or hydrogenocarbonate of said metal in said medium. Said method is particularly useful for recuperating lithium, calcium, strontium, barium, zinc, manganese, cadmium, copper and lead. Said method is particularly useful for treating an effluent or for recuperating metals in recycling or upgrading processes for alkaline cells and batteries.

Description

Procédé de récupération d'un métal sous forme de carbonate ou d'hydrogénocarbonate. Method for recovering a metal in the form of carbonate or hydrogen carbonate.
La présente invention concerne un nouveau procédé de récupération d'un métal sous forme de carbonate ou d'hydrogénocarbonate.The present invention relates to a new process for recovering a metal in the form of carbonate or hydrogen carbonate.
Le problème de l'extraction de différents métaux contenus dans desThe problem of extracting different metals from
I effluents industriels ou des déchets industriels se pose dans de nombreux secteurs de l'industrie, soit que l'on cherche à éliminer ces métaux pour des raisons d'environnement, soit que l'on cherche encore à récupérer ces métaux en vue de leur valorisation.I industrial effluents or industrial waste arises in many sectors of industry, either that we seek to eliminate these metals for environmental reasons, or that we still seek to recover these metals with a view to their valuation.
Ainsi, de nombreux effluents industriels contiennent des métaux en quantités non négligeables. C'est le cas, en particulier, d'effluents issus d'opérations de lavage ou de vidange de réacteurs, ou de mâchefers ou d'effluents issus de différents procédés industriels, en particulier d'effluents de procédés industriels comprenant des étapes d'électrolyse, tels que des effluents de traitement de surface. On se trouve également devant de tels problèmes dans le cadre de la récupération des métaux contenus dans des piles et accumulateurs.Many industrial effluents therefore contain metals in significant quantities. This is the case, in particular, of effluents from washing or emptying operations of reactors, or bottom ash or effluents from different industrial processes, in particular from industrial process effluents comprising stages of electrolysis, such as surface treatment effluents. We also face such problems in the recovery of metals from batteries and accumulators.
Dans différents procédés industriels de récupération des métaux, on cherche à précipiter sélectivement le métal, de façon à le séparer du milieu dans lequel il se trouve.In various industrial metal recovery processes, it is sought to selectively precipitate the metal, so as to separate it from the medium in which it is found.
On a décrit, dans le brevet f ançais FR 2 773 553, l'utilisation de CO2 dans le cadre d'un procédé complet de dépollution d'un ultrafîltrat de bain d'électrodéposition dans lequel on précipite le plomb par traitement de l'ultrafiltrat par du gaz carbonique ou par une espèce chimique produisant ce gaz ou par un carbonate. Toutefois, dans un tel procédé, on n'a pas cherché à optimiser les conditions de la précipitation du plomb, dans la mesure . où cette étape de précipitation est complétée par un traitement du surnageant au moyen d'une résine échangeuse d'ions.In French patent FR 2 773 553, the use of CO 2 has been described in the context of a complete process for the depollution of an electroplating bath ultrafiltrate in which the lead is precipitated by treatment of the ultrafiltrate by carbon dioxide or by a chemical species producing this gas or by a carbonate. However, in such a process, no attempt has been made to optimize the conditions for the precipitation of lead, in the measurement. where this precipitation step is completed by treatment of the supernatant with an ion exchange resin.
La présente invention propose un moyen particulièrement simple et efficace pour récupérer avec la sélectivité et le rendement désirés un métal dans un milieu aqueux.The present invention provides a particularly simple and effective means for recovering with the desired selectivity and yield a metal in an aqueous medium.
L'invention s'applique à tous les milieux dans lesquels le métal se trouve initialement sous forme dTiydroxyde ou est susceptible de se transformer en hydroxyde notamment par action d'une base forte. L'invention consiste à transformer le métal en hydroxyde lorsqu'il n'est pas sous cette forme initialement dans le milieu à traiter et à amener, le cas échéant, le pH du milieu à une valeur définie permettant de transformer Ωiydroxyde en carbonate par injection de CO2, ladite injection se faisant dans des conditions contrôlées où l'on amène ce carbonate ou cet hydrogenocarbonate à son minimum de solubilité dans le milieu. L'invention est principalement basée sur le fait que la solubilité des métaux varie avec le pH et la nature des ions présents dans le milieu (effet d'ions communs) et repose sur le fait qu'il est possible de prédéterminer la valeur du pH à laquelle il faut amener le milieu pour que rhydrogénocarbonate ou le carbonate formé par injection de CO2 se trouve à son minimum de solubilité, permettant ainsi de précipiter au mieux le métal sous la forme de carbonate ou d'hydrogénocarbonate.The invention applies to all environments in which the metal is initially found in the form of hydroxide or is capable of transforming into hydroxide in particular by the action of a strong base. The invention consists in transforming the metal into hydroxide when it is not in this form initially in the medium to be treated and in bringing, if necessary, the pH of the medium to a value defined to transform Ωiydroxide into carbonate by injection of CO 2 , said injection being carried out under controlled conditions where this carbonate or this hydrogenocarbonate is brought to its minimum solubility in the medium. The invention is mainly based on the fact that the solubility of metals varies with the pH and the nature of the ions present in the medium (effect of common ions) and is based on the fact that it is possible to predetermine the pH value to which the medium must be brought so that the hydrogen carbonate or the carbonate formed by injection of CO 2 is at its minimum of solubility, thus making it possible to precipitate the metal as best as possible in the form of carbonate or hydrogen carbonate.
Ainsi, selon l'une de ses caractéristiques essentielles, l'invention concerne un procédé de traitement d'un milieu aqueux contenant un métal sous forme dliydroxyde ou susceptible de se transformer en hydroxyde par introduction d'une base dans ledit milieu, ledit traitement étant destiné à récupérer ledit métal sous forme de carbonate ou d'hydrogénocarbonate, caractérisé en ce qu'il comprend une étape d'injection de dioxyde de carbone en quantité suffisante pour amener le pH dudit milieu à une valeur prédéterminée.Thus, according to one of its essential characteristics, the invention relates to a process for treating an aqueous medium containing a metal in the form of hydroxide or capable of transforming into hydroxide by the introduction of a base into said medium, said treatment being intended to recover said metal in the form of carbonate or hydrogen carbonate, characterized in that it comprises a step of injecting carbon dioxide in an amount sufficient to bring the pH of said medium to a predetermined value.
Différents cas peuvent se présenter en fonction de la nature du métal et du milieu concerné. La valeur prédéterminée du pH final de précipitation du carbonate ou de rhydrogénocarbonate métallique est déterminée expérimentalement et/ou à partir des connaissances de l'homme du métier concernant la solubilité du carbonate ou de l'hydrogénocarbonate du métal que l'on cherche à récupérer en fonction du pH et est avantageusement déterminée pour obtenir le rrώiimum de solubilité du carbonate ou de l'hydrogénocarbonate dudit métal dans ledit milieu.Different cases can arise depending on the nature of the metal and the medium concerned. The predetermined value of the final precipitation pH of the carbonate or metal hydrogen carbonate is determined experimentally and / or from the knowledge of a person skilled in the art concerning the solubility of the carbonate or the hydrogen carbonate of the metal which it is sought to recover in function of the pH and is advantageously determined to obtain the rrώiimum solubility of the carbonate or hydrogen carbonate of said metal in said medium.
Ainsi, la détermination du pH où le carbonate ou l'hydrogénocarbonate est au minimum de sa solubilité dans le milieu concerné peut se faire par injection dans un milieu contenant lriydroxyde correspondant, du dioxyde de carbone en surveillant le pH de façon à obtenir en fin d'injection la valeur du pH correspondant à ce minimum de solubilité recherchée.Thus, the determination of the pH where the carbonate or hydrogen carbonate is at least of its solubility in the medium concerned can be done by injection into a medium containing the corresponding hydroxide, carbon dioxide by monitoring the pH so as to obtain at the end of injection the pH value corresponding to this desired minimum solubility.
Comme exposé précédemment, l'introduction d'une base dans le milieu à traiter préalablement à l'introduction du dioxyde de carbone n'est faite que pour s'assurer à la fois que l'on se trouve initialement à un pH supérieur à la valeur prédéterminée du pH permettant la précipitation optimale désirée du carbonate ou de rhydrogénocarbonate et que le métal se trouve avant sa transformation par CO2 sous la forme d'un hydroxyde. Pour déterminer les conditions optimales à réaliser au moment de l'injection de CO2, l'homme du métier utilise ses connaissances fondamentales concernant le caractère acide ou basique de l'hydroxyde métallique du métal qu'il cherche à récupérer. Il tient en particulier compte de ce que le facteur essentiel déterminant le caractère acide ou basique d'un hydroxyde est le pouvoir polarisant de l'atome métallique qui dépend de la taille de l'atome et de son degré d'oxydation.As explained above, the introduction of a base into the medium to be treated prior to the introduction of carbon dioxide is only done to ensure that both we are initially at a pH higher than the predetermined pH value allowing the desired optimal precipitation of the carbonate or of the hydrogen carbonate and that the metal is present before its transformation by CO 2 in the form of a hydroxide. To determine the optimal conditions to be achieved at the time of CO 2 injection, the skilled person uses his fundamental knowledge concerning the acidic or basic character of the metal hydroxide of the metal which he seeks to recover. It takes into account in particular that the essential factor determining the acidic or basic character of a hydroxide is the polarizing power of the metallic atom which depends on the size of the atom and its degree of oxidation.
Ainsi, en fonction du pH initial du milieu à traiter et de la nature du métal à récupérer, on lui fait subir ou non une première étape de traitement alcalin. Ce traitement alcalin consiste à augmenter le pH du milieu à traiter, par exemple avec de la potasse, de la soude ou tout autre base forte permettant d'amener le pH à une valeur supérieure à la valeur prédéterminée de précipitation du métal sous forme de carbonate ou d'hydrogénocarbonate et à transformer le métal initialement en solution sous forme dTiydroxyde. Le CO2 est ensuite introduit dans le milieu à traiter, de façon à provoquer par un effet d'ions communs la précipitation, selon le métal à traiter, soit de son carbonate soit de son hydrogenocarbonate.Thus, depending on the initial pH of the medium to be treated and the nature of the metal to be recovered, it is subjected or not to undergo a first alkaline treatment step. This alkaline treatment consists in increasing the pH of the medium to be treated, for example with potash, soda or any other strong base allowing the pH to be brought to a value higher than the predetermined value of precipitation of the metal in the form of carbonate. or hydrogen carbonate and transforming the metal initially into solution in the form of hydroxide. The CO 2 is then introduced into the medium to be treated, so as to cause precipitation by a common ion effect, depending on the metal to be treated, either of its carbonate or of its hydrogenocarbonate.
L'introduction de CO2 est réalisée dans des conditions telles que le pH final du milieu correspond à une valeur prédéterminée, cette valeur permettant de précipiter le carbonate ou l'hydrogénocarbonate avec la sélectivité et/ou le rendement de récupération désiré. Généralement, on choisit cette valeur de façon à ce que la précipitation soit la plus complète possible, c'est-à-dire à ce que la solubilité de ce carbonate ou de cet hydrogenocarbonate soit minimale dans le milieu. Comme exposé précédemment, le dioxyde de carbone est dans tous les cas injecté dans un milieu qui se trouve à un pH supérieur à celui de la valeur prédéterminée à laquelle on souhaite amener le pH par introduction de ce CO2. Pour atteindre ces conditions initiales, il faut, dans certains cas, injecter une base. L'effet de cette base est à la fois de modifier le pH avant l'injection du dioxyde de carbone mais aussi, le cas échéant, de transformer le métal en hydroxyde.The introduction of CO 2 is carried out under conditions such that the final pH of the medium corresponds to a predetermined value, this value making it possible to precipitate the carbonate or the hydrogen carbonate with the selectivity and / or the desired recovery yield. Generally, this value is chosen so that the precipitation is as complete as possible, that is to say that the solubility of this carbonate or this hydrogenocarbonate is minimal in the medium. As explained above, carbon dioxide is in all cases injected into a medium which is at a pH higher than that of the predetermined value to which it is desired to bring the pH by introduction of this CO 2 . To reach these initial conditions, it is necessary, in certain cases, to inject a base. The effect of this base is both to modify the pH before the injection of carbon dioxide but also, if necessary, to transform the metal into hydroxide.
Il peut s'avérer nécessaire, lorsque cet hydroxyde n'est pas soluble dans le miheu à traiter, d'introduire cette base immédiatement avant l'injection de CO2, de façon à perturber le moins possible la réaction entre l'hydroxyde et le dioxyde de carbone. Ainsi donc, il suffit de contrôler le pH du miheu pendant l'introduction du dioxyde de carbone dans le milieu de façon à arrêter cette introduction lorsque la valeur prédéterminée du pH sera atteinte.It may prove necessary, when this hydroxide is not soluble in the medium to be treated, to introduce this base immediately before the injection of CO 2 , so as to disturb the reaction between the hydroxide and the carbon dioxide. Thus, it suffices to control the pH of the medium during the introduction of carbon dioxide into the medium so as to stop this introduction when the predetermined pH value is reached.
L'injection de CO2 est réalisée tant que la valeur de consigne du pH n'est pas atteinte. Cette introduction est arrêtée dès que l'on atteint la valeur de consigne.CO 2 injection is carried out as long as the pH setpoint is not reached. This introduction is stopped as soon as the setpoint is reached.
Parallèlement, et cela afin de valider la valeur de consigne du pH, on effectue avantageusement, en fin d'injection, un prélèvement d'un échantillon de liquide à traiter sur lequel on effectue une analyse permettant de quantifier la concentration en métal dissous dans le liquide et, cela, afin de s'assurer que l'on se trouve à une concentration résiduelle en métal acceptable.At the same time, and in order to validate the pH setpoint, advantageously, at the end of injection, a sample of the liquid to be treated is taken, on which an analysis is carried out making it possible to quantify the concentration of dissolved metal in the liquid, and this in order to ensure that we are at an acceptable residual metal concentration.
L'invention est applicable à tous les métaux susceptibles d'être précipités sous une forme de carbonate ou d'hydrogénocarbonate à partir de leur hydroxyde par introduction de CO2 dans un milieu alcalin les contenant. Elle s'applique tout particulièrement aux métaux alcalins et, en particulier, au Hthium, aux métaux alcalino-terreux et, en particulier, au calcium, au strontium, au magnésium et au baryum. Elle s'applique également au zinc, au manganèse, au cadmium, au cuivre et au plomb.The invention is applicable to all metals capable of being precipitated in the form of carbonate or hydrogen carbonate from their hydroxide by the introduction of CO 2 into an alkaline medium containing them. It applies very particularly to alkali metals and, in particular, to Hthium, to alkaline earth metals and, in particular, to calcium, to strontium, to magnesium and to barium. It also applies to zinc, manganese, cadmium, copper and lead.
En fonction du métal à récupérer, si les deux formes carbonate et hydrogenocarbonate existent, on cherche à récupérer soit le carbonate, soit l'hydrogénocarbonate, en fonction de celle qui peut être le plus sélectivement précipitée.Depending on the metal to be recovered, if the two forms carbonate and hydrogenocarbonate exist, we seek to recover either the carbonate or the hydrogen carbonate, depending on which can be the most selectively precipitated.
L'homme du métier est capable de déterminer les conditions optimales de précipitation de la forme visée de ce métal et de les compléter par des essais expérimentaux pour fixer le pH servant de valeur de consigne lors de l'injection de CO2.A person skilled in the art is capable of determining the optimal conditions for precipitation of the target form of this metal and of supplementing them by experimental tests to fix the pH serving as a reference value during the injection of CO 2 .
Le dioxyde de carbone peut être injecté soit sous forme gazeuse, soit sous forme liquide.Carbon dioxide can be injected either in gaseous form or in liquid form.
Cette injection peut se faire soit directement dans le miheu aqueux à traiter, soit indirectement dans une boucle de recirculation prévue à cet effet.This injection can be done either directly in the aqueous medium to be treated, or indirectly in a recirculation loop provided for this purpose.
Dans tous les cas, le dioxyde de carbone se transforme en acide carbonique qui est un diacide faible présentant une courbe de neutralisation à pente douce.In all cases, the carbon dioxide is transformed into carbonic acid which is a weak diacid presenting a neutralization curve with a gentle slope.
Pour assurer une meilleure efficacité du traitement par le dioxyde de carbone, le miheu à traiter est, si nécessaire, soumis à une agitation pendant le traitement au CO2. Cette agitation est ensuite soit arrêtée pour assurer une meilleure précipitation du carbonate ou de l'hydrogénocarbonate formé soit maintenue si l'on cherche à conserver le précipité en suspension pendant la durée du traitement.To ensure better effectiveness of the treatment with carbon dioxide, the medium to be treated is, if necessary, subjected to agitation during the treatment with CO 2 . This agitation is then either stopped to ensure a better precipitation of the carbonate or hydrogen carbonate formed is maintained if one seeks to keep the precipitate in suspension for the duration of the treatment.
Différents avantages sont liés à l'utilisation de dioxyde de carbone. En particuher, il n'y a lors de l'utilisation du dioxyde de carbone aucun risque de suracidification du miheu pouvant porter préjudice à la resolubilisation d'ions métalliques dans le liquide traité. Par ailleurs, l'utilisation de dioxyde de carbone permet une régulation extrêmement précise du pH. Il est en effet possible de contrôler le pH à un lOème prés, ce qui permet dans la plupart des cas d'obtenir une précipitation sélective du métal sous la forme désirée (carbonate pu hydrogenocarbonate) .There are different benefits associated with the use of carbon dioxide. In particular, there is no risk of over-acidification of the miheu during the use of carbon dioxide which could harm the resolubilization of metal ions in the treated liquid. In addition, the use of carbon dioxide allows extremely precise regulation of the pH. It is indeed possible to control the pH to a lOth near, which allows in most cases to obtain a selective precipitation of the metal in the desired form (carbonate or hydrogenocarbonate).
Par ailleurs, un autre avantage de l'utilisation du CO2 est que le CO2 permet d'éviter toute pollution secondaire saline.Another advantage of using CO 2 is that CO 2 makes it possible to avoid any secondary saline pollution.
Par ailleurs, comme cela ressort de la description détaillée et des exemples qui suivent, l'invention est tout particulièrement applicable au traitement de différents effluents industriels, en vue de les débarrasser des métaux contenus avec pour souci, le respect des normes d'environnement et/ou la récupération de ces métaux en vue de leur valorisation ultérieure.Furthermore, as appears from the detailed description and from the examples which follow, the invention is very particularly applicable to the treatment of various industrial effluents, with a view to ridding them of the metals contained with concern, respect for environmental standards and / or the recovery of these metals with a view to their subsequent recovery.
L'invention s'applique également au traitement de recyclage des métaux utilisés dans l'industrie des piles et des accumulateurs, en particuher du manganèse, du zinc, du hthium, du cadmium, du plomb et du cuivre.The invention also applies to the recycling treatment of metals used in the battery and accumulator industry, in particular manganese, zinc, hthium, cadmium, lead and copper.
Dans ces deux types d'applications, on se trouve en présence de miheux aqueux contenant les métaux.In these two types of applications, we are in the presence of aqueous media containing metals.
Dans le procédé de l'invention, on traite tout d'abord, le cas échéant, ces miheux aqueux par une base forte de façon à se placer à un pH supérieur à la valeur de consigne imposée lors de l'injection de CO2 et à laquelle le métal se trouve au moins partiellement sous forme d'hydroxyde. La régulation du pH par le dioxyde de carbone se fait ensuite, suivant le cas, soit dans une bâche de neutralisation, en particuher dans le cas du traitement d'un effluent, soit dans un réacteur, en particuher dans le cas du traitement d'une solution alcaline issue de l'industrie des piles et accumulateurs.In the process of the invention, these aqueous mediums are first of all treated, if necessary, with a strong base so as to be placed at a pH higher than the set value imposed during the injection of CO 2 and in which the metal is at least partially in the form of hydroxide. The regulation of the pH by carbon dioxide is then done, as the case may be, either in a neutralization tank, in particular in the case of the treatment of an effluent, or in a reactor, in particular in the case of the treatment of an alkaline solution from the battery and accumulator industry.
Par des tests préalables, on détermine la valeur de consigne du pH qui correspond au pH final à atteindre lors de l'injection du dioxyde de carbone de façon à avoir la concentration résiduelle désirée minimale de métal récupéré. Cette valeur de consigne correspond à la précipitation maximale du métal sous forme de carbonate ou d'hydrogénocarbonate et donc à la valeur minimale de la teneur en métal dissous dans le milieu.By preliminary tests, the pH set point is determined which corresponds to the final pH to be reached during the injection of carbon dioxide so as to have the minimum desired residual concentration of recovered metal. This setpoint corresponds to the maximum precipitation of the metal in the form of carbonate or hydrogen carbonate and therefore at the minimum value of the content of dissolved metal in the medium.
Le CO2 est alors injecté soit sous forme gazeuse, soit sous forme liquide dans le miheu en asservissant l'injection à la mesure du pH dans le liquide à traiter.The CO 2 is then injected either in gaseous form or in liquid form into the medium by slaving the injection to the measurement of the pH in the liquid to be treated.
On arrête ensuite l'injection de CO2 lorsque la valeur de consigne duThe CO 2 injection is then stopped when the setpoint of the
I pH est atteinte. En parallèle, on peut prélever un échantillon du liquide à traiter et effectuer une analyse permettant de quantifier la concentration en métal dissous restante dans le miheu. Les figures 1 et 2 ci-jointes illustrent deux modes de réalisation du procédé de l'invention, respectivement dans le cas où la neutralisation est faite dans une bâche (figure 1) et où le procédé est mis en oeuvre dans un réacteur agité (figure 2).I pH is reached. In parallel, we can take a sample of the liquid to be treated and perform an analysis to quantify the concentration of dissolved metal remaining in the medium. Figures 1 and 2 attached illustrate two embodiments of the process of the invention, respectively in the case where the neutralization is done in a tank (Figure 1) and where the process is carried out in a stirred reactor (Figure 2).
Sur le dispositif de la figure 1, un effluent à traiter est introduit par la canalisation 2 dans la bâche 1 munie d'un dispositif 4 d'agitation mécanique. Un circuit de recirculation 5 muni d'une pompe 6 permet d'assurer une recirculation de l'effluent. Ce circuit comprend un réacteur tubulaire 7 muni d'un dispositif d'injection de dioxyde de carbone par l'intermédiaire d'une électrovanne d'injection 8. Le pH du miheu à traiter est mesuré en permanence par un pHmètre 9.On the device of FIG. 1, an effluent to be treated is introduced through the pipe 2 into the tank 1 provided with a device 4 for mechanical agitation. A recirculation circuit 5 provided with a pump 6 ensures recirculation of the effluent. This circuit comprises a tubular reactor 7 fitted with a device for injecting carbon dioxide via an injection solenoid valve 8. The pH of the medium to be treated is continuously measured by a pH meter 9.
Une armoire de régulation, munie d'une alimentation électrique, permet d'assujettir l'ouverture de la vanne 8 à la mesure du pH réalisée par le pHmètre 9 de façon à fermer la vanne d'injection du CO2 lorsque la valeur de consigne du pH est atteinte.A control cabinet, fitted with an electrical supply, allows the opening of valve 8 to be subject to the pH measurement carried out by pH meter 9 so as to close the CO 2 injection valve when the set value pH is reached.
Ainsi, dans le dispositif représenté sur la figure 1, l'injection de CO2 est réalisée par recirculation d'une partie de l'effluent à traiter.Thus, in the device represented in FIG. 1, the CO 2 injection is carried out by recirculation of part of the effluent to be treated.
Cette injection peut être faite soit sous forme de CO2 hquide, soit sous forme de CO2 gazeux par des dispositifs classiques d'injection de CO2 dans un circuit.This injection can be carried out either in the form of liquid CO 2 or in the form of gaseous CO 2 by conventional devices for injecting CO 2 into a circuit.
Dans d'autres modes de réalisation également applicables au traitement d'un effluent, on peut injecter dans l'effluent à traiter directement le CO2 dans la bâche de récupération de l'effluent en recourant, par exemple, à une turbine d'injection ou à tout autre dispositif classiquement utilisé pour introduire du CO2 de façon aussi homogène que possible dans une cuve, par exemple en introduisant ce CO2 par rintermédiaire d'une ou plusieurs bougies poreuses. On a représenté sur la figure 2 un exemple de réalisation de l'invention où la solution à traiter est placée dans un réacteur agité. On a recours à un tel réacteur, en particuher pour traiter les solutions alcalines issues du traitement des piles et des accumulateurs alcalins et contenant, en solution, le métal à récupérer.In other embodiments also applicable to the treatment of an effluent, it is possible to inject the CO 2 directly into the effluent to be treated CO 2 into the effluent recovery tank by using, for example, an injection turbine. or any other device conventionally used to introduce CO 2 as homogeneously as possible into a tank, for example by introducing this CO 2 by means of one or more porous candles. FIG. 2 shows an embodiment of the invention in which the solution to be treated is placed in a stirred reactor. We use such reactor, in particular for treating alkaline solutions from the treatment of alkaline batteries and accumulators and containing, in solution, the metal to be recovered.
Dans le dispositif représenté sur cette figure, on introduit la solution alcaline contenant le métal à récupérer dans un réacteur 11 muni d'un pHmètre 9. Comme dans le cas illustré par la figure 1, on provoque une recirculation de la solution à traiter par l'intermédiaire d'un circuit de recirculation 5 comprenant unIn the device represented in this figure, the alkaline solution containing the metal to be recovered is introduced into a reactor 11 provided with a pH meter 9. As in the case illustrated by FIG. 1, the solution to be treated is recirculated by l '' through a recirculation circuit 5 comprising a
I réacteur tubulaire 7 et muni d'une pompe 6 assurant la recirculation d'une partie de la solution à traiter. Du CO2 liquide est introduit dans le réacteur tubulaire par l'intermédiaire de l'électrovanne 8 dont l'ouverture est commandée comme dans le cas précédent par l'intermédiaire d'un dispositif de régulation contenu dans une armoire de régulation 10.I tubular reactor 7 and fitted with a pump 6 ensuring the recirculation of part of the solution to be treated. Liquid CO 2 is introduced into the tubular reactor by means of the solenoid valve 8, the opening of which is controlled as in the previous case by means of a regulation device contained in a regulation cabinet 10.
Comme dans le cas illustré sur la figure 1, dans le cas illustré sur la figure 2, l'injection de CO2 peut également être faite selon le même schéma en utilisant du CO2 gazeux. On peut également envisager d'introduire dans un réacteur agité tel que celui représenté sur la figure 2 du CO2 gazeux directement dans ce réacteur en recourant à une turbine d'injection ou à des bougies poreuses.As in the case illustrated in FIG. 1, in the case illustrated in FIG. 2, the injection of CO 2 can also be carried out according to the same scheme using CO 2 gas. It is also possible to envisage introducing gaseous CO 2 directly into this reactor, using an injection turbine or porous candles, into a stirred reactor such as that shown in FIG. 2.
Les exemples qui suivent sont donnés à titre purement ilîustratif de l'invention.The examples which follow are given purely by way of illustration of the invention.
Exemple 1Example 1
Traitement d'un effluent industriel contenant du strontiumTreatment of an industrial effluent containing strontium
On traite dans un dispositif tel que représenté sur la figure 1 des eaux de rejet industriel contenant du strontium sous forme dxiydroxyde à un pH initial de 12,4. La teneur en strontium de l'effluent à traiter est de 6400 ppm.Industrial waste water containing strontium in the form of hydroxide at an initial pH of 12.4 is treated in a device as shown in FIG. 1. The strontium content of the effluent to be treated is 6400 ppm.
L'effluent est collecté dans une cuve agitée telle que représentée sur la figure 1. Le CO2 est injecté sous forme liquide ou gazeuse par recirculation d'une partie de l'effluent à traiter.The effluent is collected in a stirred tank as shown in FIG. 1. The CO 2 is injected in liquid or gaseous form by recirculating part of the effluent to be treated.
Dans le cas présent, le but visé est d'amener la teneur en strontium à une valeur inférieure à 1 ppm de façon à respecter la norme en vigueur concernant les teneurs autorisées en ce métal dans un effluent.In the present case, the aim is to bring the strontium content to a value of less than 1 ppm so as to comply with the standard in force concerning the authorized contents of this metal in an effluent.
Le traitement est réalisé à la pression atmosphérique et à température ambiante.The treatment is carried out at atmospheric pressure and at ambient temperature.
La valeur de consigne du pH est fixée à 9 de façon à obtenir une précipitation maximale du carbonate de strontium et à atteindre une valeur minimale en strontium dissous de 0,6 ppm. Une mesure de la concentration résiduelle en métal après traitement en CO2 est réalisée par une technique d'émission de flamme.The pH setpoint is fixed at 9 so as to obtain maximum precipitation of the strontium carbonate and to reach a minimum dissolved strontium value of 0.6 ppm. A measurement of the residual metal concentration after treatment with CO 2 is carried out by a flame emission technique.
On observe que la précipitation commence par la formation de germes cristallins par association de quelques ions. Plus la solution est concentrée et aussi moins le composé est soluble, plus les germes sont nombreux dans un temps donné. IIt is observed that precipitation begins with the formation of crystal seeds by association of a few ions. The more the solution is concentrated and also the less the compound is soluble, the more the germs are numerous in a given time. I
Par ailleurs, la formation de germes est nettement accélérée par l'agitation. L'agitation permet de maintenir le précipité en suspension dès sa formation, ce qui permet de l'extraire en fin de réaction. Le précipité extrait est ensuite essoré et filtré.Furthermore, the formation of germs is significantly accelerated by agitation. Stirring keeps the precipitate in suspension as soon as it forms, which makes it possible to extract it at the end of the reaction. The extracted precipitate is then drained and filtered.
Exemple 2Example 2
Recyclage des métaux contenus dans les piles et accumulateursRecycling of metals contained in batteries and accumulators
Les piles sont, dans un premier temps, broyées, les matériaux actifs sont ensuite séparés des boîtiers métalhques par criblage mécanique. Les matériaux actifs sont ensuite mis en solution en miheu alcalin. Ce sont des solutions alcalines de ce type qui sont traitées dans les exemples 2a et 2b ci-après.The batteries are first crushed, the active materials are then separated from the metal housings by mechanical screening. The active materials are then dissolved in an alkaline medium. These are alkaline solutions of this type which are treated in Examples 2a and 2b below.
Exemple 2a Récupération du zincEXAMPLE 2 Zinc Recovery
On traite une solution alcaline contenant du zinc dissous dans un réacteur du type de celui représenté sur la figure 2.An alkaline solution containing zinc dissolved in a reactor of the type shown in FIG. 2 is treated.
La valeur de consigne du pH final à atteindre lors de l'injection de CO2 est de 8, de façon à obtenir de l'hydrogénocarbonate de zinc.The final pH setpoint to be reached during the CO 2 injection is 8, so as to obtain zinc hydrogen carbonate.
Exemple 2b Récupération du manganèseEXAMPLE 2 Recovery of Manganese
On traite une solution issue d'un traitement de déchets de pile en réacteur agité. La solution traitée se trouve initialement à un pH acide compris entre 4 et 5. On injecte dans cette solution de la soude de façon à transformer progressivement le manganèse en hydroxyde de manganèse, puis on injecte du CO2 en affichant une valeur de consigne du pH de 8,5. Plus précisément, le procédé est mis en œuvre, à la température ambiante et sous la pression atmosphérique, dans un réacteur agité du type de celui représenté sur la figure 2. La soude est introduite dans cet exemple dans le réacteur tubulaire 7 en amont du point d'introduction du CO2. Par ailleurs, un mélangeur statique en hgne (non représenté sur la figure 2) permet d'améhorer le contact. L'ensemble de ces conditions permet de rendre quasi instantanée la transformation en carbonate dès la formation de l'hydroxyde et d'éviter les inconvénients qui résulteraient de la précipitation de l'hydroxyde dans le miheu. A solution from a treatment of cell waste in a stirred reactor is treated. The treated solution is initially at an acidic pH of between 4 and 5. In this solution, sodium hydroxide is injected so as to gradually transform the manganese into manganese hydroxide, then CO 2 is injected by displaying a pH setpoint. 8.5. More specifically, the process is carried out, at ambient temperature and under atmospheric pressure, in a stirred reactor of the type shown in FIG. 2. The sodium hydroxide is introduced in this example into the tubular reactor 7 upstream of the point CO 2 introduction. In addition, a static mixer in hgne (not shown in FIG. 2) makes it possible to improve the contact. All of these conditions make it possible to make the transformation into carbonate almost instantaneous as soon as the hydroxide is formed and to avoid the drawbacks which would result from the precipitation of the hydroxide in the medium.

Claims

REVENDICATIONS
1. Procédé de traitement d'un miheu aqueux contenant un métal sous forme d'hydroxyde ou susceptible de se transformer en hydroxyde par introduction d'une base dans ledit miheu, ledit traitement étant destiné à récupérer ledit métal sous forme de carbonate ou d'hydrogénocarbonate, caractérisé en ce qu'il comprend une étape d'injection de dioxyde de carbone en quantité suffisante pour amener le pH dudit miheu à une valeur prédéterminée correspondant au minimum de solubilité du carbonate ou de l'hydrogénocarbonate dudit métal dans ledit miheu.1. A method of treating an aqueous miheu containing a metal in the form of hydroxide or capable of transforming into hydroxide by the introduction of a base into said miheu, said treatment being intended to recover said metal in the form of carbonate or hydrogen carbonate, characterized in that it comprises a step of injecting carbon dioxide in sufficient quantity to bring the pH of said miheu to a predetermined value corresponding to the minimum solubility of the carbonate or hydrogen carbonate of said metal in said miheu.
2. Procédé selon la revendication 1, caractérisé en ce que ladite injection de dioxyde de carbone est précédée d'une étape d'introduction d'une base dans ledit miheu destinée à amener le pH à une valeur supérieure à ladite valeur prédéterminée et/ou à transformer ledit métal en hydroxyde. 2. Method according to claim 1, characterized in that said injection of carbon dioxide is preceded by a step of introducing a base into said miheu intended to bring the pH to a value greater than said predetermined value and / or transforming said metal into hydroxide.
3. Procédé selon l'une des revendications 1 ou 2, caractérisé en ce qu'il comprend en outre une étape complémentaire de contrôle de la concentration résiduelle du métal en solution lorsque ladite valeur prédéterminée a été atteinte.3. Method according to one of claims 1 or 2, characterized in that it further comprises an additional step of controlling the residual concentration of the metal in solution when said predetermined value has been reached.
4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce que ledit métal est choisi dans le groupe constitué du hthium, du calcium, du strontium, du baryum, du zinc, du manganèse, du cadmium, du cuivre, et du plomb.4. Method according to one of claims 1 to 3, characterized in that said metal is chosen from the group consisting of hthium, calcium, strontium, barium, zinc, manganese, cadmium, copper, and Lead.
5. Procédé selon l'une des revendications 1 à 4, caractérisé en ce que ladite injection de CO2 est faite par l'intermédiaire de CO2 gazeux.5. Method according to one of claims 1 to 4, characterized in that said injection of CO 2 is made via CO 2 gas.
6. Procédé selon l'une des revendications 1 à 5, caractérisé en ce que ladite injection de CO2 est faite par l'intermédiaire de CO2 liquide. 6. Method according to one of claims 1 to 5, characterized in that said injection of CO 2 is made via liquid CO 2 .
7. Procédé selon l'une des revendications 1 à 6 caractérisé en ce que ladite injection de CO2 est faite directement dans le miheu aqueux à traiter ou indirectement dans une boucle de recirculation prévue à cet effet.7. Method according to one of claims 1 to 6 characterized in that said injection of CO 2 is made directly into the aqueous medium to be treated or indirectly in a recirculation loop provided for this purpose.
8. Procédé de traitement d'un effluent, en particuher d'un effluent industriel contenant un métal sous forme d'hydroxyde ou susceptible d'être transformé en hydroxyde par introduction d'une base forte dans ledit effluent, caractérisé en ce qu'il consiste à appliquer audit effluent un procédé tel que défini dans l'une des revendications 1 à 7.8. Process for treating an effluent, in particular an industrial effluent containing a metal in the form of hydroxide or capable of being transformed into hydroxide by the introduction of a strong base into said effluent, characterized in that it consists in applying to said effluent a process as defined in one of claims 1 to 7.
9. Procédé selon la revendication 8, caractérisé en ce que ledit effluent est, dans une première étape, collecté dans une cuve (1), l'injection de CO2 se faisant soit directement dans ladite cuve sous forme gazeuse, soit indirectement sous forme gazeuse ou liquide dans un circuit (5) de recirculation dudit effluent. 9. Method according to claim 8, characterized in that said effluent is, in a first step, collected in a tank (1), the CO 2 injection being carried out either directly in said tank in gaseous form, or indirectly in the form gas or liquid in a recirculation circuit (5) of said effluent.
10. Procédé selon l'une des revendications 8 ou 9, caractérisé en ce que ledit métal à récupérer est le strontium et en ce que la valeur prédéteπninée est déterminée de façon à obtenir une précipitation niaximale du strontium sous forme de carbonate de strontium.10. Method according to one of claims 8 or 9, characterized in that said metal to be recovered is strontium and in that the predefined value is determined so as to obtain a niaximal precipitation of strontium in the form of strontium carbonate.
11. Procédé pour récupérer un métal, en particuher le hthium, le zinc, le plomb, le manganèse, le cuivre ou le cadmium dans une solution alcaline issue d'une étape de recyclage ou de revalorisation de piles et/ou d'accumulateurs alcalins, caractérisé en ce qu'il comprend l'apphcation à ladite solution alcaline d'un procédé tel que défini dans l'une des revendications 1 à 7. 11. Method for recovering a metal, in particular hthium, zinc, lead, manganese, copper or cadmium in an alkaline solution resulting from a step of recycling or upgrading of alkaline batteries and / or accumulators , characterized in that it comprises the application to said alkaline solution of a process as defined in one of claims 1 to 7.
PCT/FR2001/001675 2000-05-31 2001-05-30 Method for recuperating a metal in carbonate or hydrogenocarbonate form WO2001092152A1 (en)

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WO2003086973A1 (en) * 2002-04-05 2003-10-23 Bertshell Pty Ltd Process and apparatus for use in preparing an aqueous magnesium bicarbonate solution
WO2008128545A1 (en) * 2007-04-20 2008-10-30 Omya Development Ag Process for production of pcc
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CN115744992A (en) * 2022-12-23 2023-03-07 四川长虹格润环保科技股份有限公司 Method for separating lithium and transition metal
CN115744992B (en) * 2022-12-23 2024-05-07 四川长虹格润环保科技股份有限公司 Separation method of lithium and transition metal

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