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    • 专利摘要:
    The invention relates to a process for recovering platinum from a material in which it is contained, this process comprising an electrolysis step conducted in an electrolytic solution in which is immersed a system comprising a positive electrode and an electrode negative connected to a device for controlling the potential of one of the two positive and negative electrodes, the material being disposed on the positive electrode and the electrolyte solution comprising a first ionic liquid LI1. LI1 is formed by a first organic cation and a first inorganic anion selected from the group consisting of halide anions, dicyanamides and thiocyanates, and the electrolytic solution further comprises a second LI2 ionic liquid formed by a second organic cation and a second anion selected from the group consisting of anions TFSI-, FSI-, CF3SO3-, FAP- and BOB-, whereby platinum is recovered on the negative electrode. The invention also relates to a method for recovering platinum contained in fuel cell electrodes that implements the above method.
    公开号:FR3053364A1
    申请号:FR1656293
    申请日:2016-07-01
    公开日:2018-01-05
    发明作者:Emmanuel Billy；Maxime Balva；Natalie Leclerc；Sophie Legeai；Eric Meux
    申请人:Commissariat a lEnergie Atomique CEA；Universite de Lorraine；Commissariat a lEnergie Atomique et aux Energies Alternatives CEA；
    IPC主号:
    专利说明:

    Holder (s): COMMISSIONER FOR ATOMIC ENERGY AND ALTERNATIVE ENERGIES Public establishment, UNIVERSITY OF LORRAINE Public establishment.
    Extension request (s)
    Agent (s): BREVALEX Limited liability company.
    FR 3 053 364 - A1 (54) METHOD FOR RECOVERING PLATINUM, ELECTROCHEMICALLY, FROM A MATERIAL IN WHICH IT IS CONTAINED.
    The invention relates to a process for recovering platinum from a material in which it is contained, this process comprising an electrolysis step carried out in an electrolytic solution in which a system comprising a positive electrode is immersed and a negative electrode connected to a device making it possible to control the potential of one of the two positive and negative electrodes, the material being placed on the positive electrode and the electrolytic solution comprising a first ionic liquid
    READ.
    LU is formed by a first organic cation and a first inorganic anion chosen from the group consisting of halide, dicyanamide and thiocyanate anions, and the electrolytic solution further comprises a second ionic liquid LI2 formed by a second organic cation and a second anion chosen from the group consisting of TFSI, FSI, CF3SO3, FAP and BOB 'anions, whereby the platinum is recovered on the negative electrode.
    The invention also relates to a method for recovering platinum contained in fuel cell electrodes which implements the above method.
    METHOD FOR RECOVERING PLATINUM, ELECTROCHEMICALLY, FROM A MATERIAL IN WHICH IT IS CONTAINED
    DESCRIPTION
    TECHNICAL AREA
    The present invention relates to a process for recovering platinum from a material in which this platinum is contained.
    It relates more particularly to a process for the recovery, by electrochemical means, of platinum from such a material, this recovery process comprising an electrolysis step carried out in a particular electrolytic solution.
    The material from which the platinum can be recovered can in particular be a fuel cell electrode comprising said platinum.
    The present invention finds particular application in the recycling of fuel cells reaching the end of their life, in particular of fuel cells with a proton exchange membrane, with a view to recovering the platinum present in the latter.
    PRIOR STATE OF THE ART
    Proton exchange membrane fuel cells (in English, Proton Exchange Membrane Fuel Cells and abbreviated PEMFC) transform the chemical energy released during the electrochemical reaction of dihydrogen (H 2 ) and dioxygen (O 2 ) into electrical energy.
    PEMFC type batteries consist of a stack of elementary electrochemical cells which are separated from each other by bipolar plates. These elementary electrochemical cells, also called membrane electrode assemblies and abbreviated AME, are formed by a membrane disposed between two electrodes, this membrane acting as an electrolyte by blocking the passage of electrons and allowing H + ions to pass. The electrodes of these MEAs include a catalyst, generally based on noble metals such as platinum, making it possible to catalyze the oxidation reaction of dihydrogen.
    If we consider all the components forming a fuel cell of the PEMFC type, the cost of platinum alone represents 25% of the overall cost of such a cell.
    Also, and so that the cost of platinum does not constitute a brake on the development of PEMFC type battery technology, there is a strong interest in implementing an efficient and economically viable process for recovering platinum and, in particular, the platinum contained in end-of-life fuel cell MEAs and / or production scrap.
    To date, the recovery of platinum present in catalytic systems is ensured, on an industrial scale, either by pyrometallurgical processes, or by hydrometallurgical processes.
    The recovery of platinum by the pyrometallurgical route consists in bringing to a very high temperature, in a plasma arc furnace, a mixture comprising this catalytic system, previously ground, and a flux, these temperatures being typically between 1400 ° C. and 1700 ° C. .
    If the pyrometallurgical processes are effective in recovering platinum, they have the disadvantage of consuming a lot of energy and leading to the release of significant quantities of gases which are harmful to man and the environment. In particular, these pyrometallurgical processes lead to the formation of carbon dioxide (CO2) but can also lead to the formation of toxic gases. Among these toxic gases, there may be mentioned sulfur dioxide (SO2) or also hydrogen fluoride (HF), these two gases originating from the combustion of the membrane of ΓΑΜΕ, when the latter is made of a perfluorocarbon polymer and comprising sulfonated groups, such as the polymer known under the name Nation ™ and available from the company DuPont de Nemours.
    In addition, the pyrometallurgical processes do not make it possible to recover the other components which constitute the MEAs.
    The recovery of platinum by the hydrometallurgical route consists in bringing the catalytic system, previously ground, into contact with a solution aimed at dissolving and then recovering the platinum. The solution which is recognized, to date, as being the most effective in dissolving platinum is aqua regia, which is formed by a concentrated mixture of hydrochloric acid and nitric acid in a 1/3 ratio.
    While they make it possible to recover, in addition to platinum, other constituent components of MEAs and, in particular, membranes, graphite or carbon electrodes, hydrometallurgical processes nevertheless present significant risks linked to the use of mixtures concentrated acids and the subsequent treatment of aqueous effluents, which generates additional costs in terms of industrial safety which can jeopardize the economic balance of such processes.
    To overcome the drawbacks of the pyrometallurgical and hydrometallurgical processes which have just been mentioned, new methods have been proposed for recovering platinum from a material in which this platinum is contained electrochemically.
    Such platinum recovery methods include an electrolysis step conducted in an electrolytic solution in which is immersed a system comprising a positive electrode and a negative electrode and connected to a device allowing the application of a potential difference between the electrodes positive and negative, the material containing the platinum being placed on the positive electrode and the electrolytic solution comprising an ionic liquid.
    As clearly established by the scientific literature, an ionic liquid is a salt having a melting temperature less than or equal to 100 ° C and often even less than room temperature. An ionic liquid, which typically consists of an organic cation and an organic or inorganic anion, is characterized by high thermal stability, by almost zero vapor pressure as well as by very low flammability, which has a real advantage in terms of industrial implementation.
    Various electrolytic solutions, all comprising an ionic liquid and a compound in solution, such as a salt, have thus been proposed.
    The publication by J.-F. Huang et al. (Heat-Assisted Electrodissolution of Platinum in an Ionie Liquid, Angewandte Communications, 2012, 51, 1684-1688), referenced [1] at the end of this description, offers an electrolytic solution comprising, as ionic liquid, chloride of l -ethyl-3-methylimidazolium (abbreviated [EMIM] [Cl]) and, as salt in solution, zinc chloride ZnCh, in a molar ratio 75/25. Publication [1] reports that the implementation of such an electrolytic solution has made it possible to obtain:
    on the one hand, the anodic dissolution of the metallic platinum constituting the anode, the majority anodization product thus formed being constituted by Pt + lv ions found in the electrolytic solution, and
    - on the other hand, the direct and effective recovery by electrodeposition, at the cathode, of metallic platinum by reduction of these Pt 4+ ions present in the electrolytic solution.
    The publication by C. Deferm et al. (Electrochemical dissolution of metallic platinum in ionic liquids, J. Appl. Electrochem., 2013, 43, 797-804), referenced [2], offers several alternative electrolytic solutions, presented as less expensive than the electrolytic solution of the publication [1 ], Among the different electrolytic solutions envisaged by this publication [2], only the electrolytic solution comprising choline chloride (abbreviated [Ch] [CI]) as ionic liquid and zinc chloride ZnCh as salt in solution, in a report 50/50 molar, has proved satisfactory for allowing the anodic dissolution of platinum and the formation of a metal deposit at the cathode.
    However, publication [2] reports that the choice of material for the cathode has an influence, not only on the efficiency of the anodic dissolution of platinum, but also on the nature of the metallic deposit at this cathode. In particular, it is not conceivable to use a stainless steel cathode, this stainless steel being effectively corroded by the electrolytic solution [Ch] [Clj / ZnCb. When a cathode of indium oxide doped with tin (in English, indium tin oxide, abbreviated ITO), a deposit of metallic platinum is obtained at the cathode, deposit which is in the form of dendrites. On the other hand, in the presence of an ITO cathode, the yield of the anodic dissolution is only 15% and, moreover, a release of dichlorine gas (Ch) is observed at the anode. When a titanium cathode is used, the anodic dissolution yield increases to 96% and no release of Ch is observed. However, in this case, the metallic deposit obtained at the cathode is formed by a layer of zinc comprising minimal traces of metallic platinum, the metallic platinum being in turn in the form of powder in the electrolytic solution.
    The document WO 2006/074523 A1, referenced [3], relates to a process for recovering platinoids by means of an electrolytic solution comprising an ionic liquid.
    This document [3] describes that the ionic liquid can be chosen from a wide range of ionic liquids resulting from the combination of one of the cations with one of the following anions:
    - for cations: tetraalkylammonium, Ν, Ν-dialkylimidazolium, N, Ndialkylpyrrolidinium, tetraalkylphosphonium, N-alkylpyridinium and N, Ndialkylpiperidinium;
    - for anions: Cl, Br, AICL, BFy, PF6, NO3 ', alkylsulfonate (RSO3), alkylthiol (RS), dithiocarbamate (RNCS2), xanthate (ROCS2), acetate, trifluoroacetate, substituted sulfonate, tetracyanoborate, alkylsulfate, bis (trifluoromethylsulfonyl) imide (abbreviated TFSI), bis (trifluoromethyl) imide (abbreviated TFI) and dicyanamide.
    However, it should be noted that the examples described in this document [3] in relation to the dissolution of a platinum anode and the recovery of platinum at the cathode were all carried out with 1-methyl-1-butylpyrrolidinium methanesulfonate (abbreviated [P14ÏÏCH3SO3]) as an ionic liquid. Were thus tested electrolytic solutions comprising [P14ÏÏCH3SO3] with aluminum nitrate AI (NÜ3) 3, hydrated hexachloroplatinic acid FhPtCle.GFhO or ammonium nitrate NH4NO3 in solution.
    Depending on the nature of the compound in solution retained, the composition of the metal deposit obtained at the cathode differs. If a deposit of metallic platinum is obtained on the vitreous carbon cathode with the electrolytic solutions [Pi4] [CH3SO3] /H2PtCl6.6H2O and [P14ÏÏCH3SO3VNH4NO3, a metallic deposit is obtained comprising, as majority component, platinum but comprising also silver and aluminum with the electrolytic solution [P14] [CH3SO3] / AI (NC> 3) 3 If the platinum recovery processes by electrochemical way as taught by publications [1] to [3 ] overcome the major drawbacks of pyrometallurgical and hydrometallurgical processes, the fact remains that they are not entirely satisfactory, in particular in terms of reproducibility and environmental safety. In particular, the reactions occurring at the anode are not always controlled and can produce gases which are particularly harmful to humans and the environment, such as nitrogen oxides, known under the generic name of NOx gases, in particular particularly when the compound in solution in the electrolytic solution consists of aluminum or ammonium nitrate, as in the publication [3].
    It is on the basis of this observation that the inventors have set themselves the goal of providing a new process for recovering platinum from a material in which it is contained, this process always being carried out electrochemically by means of 'an electrolytic solution, but not presenting the drawbacks noted above with the implementation of the electrolytic solutions proposed in publications [1] to [3].
    This new platinum recovery process must, in particular, be able to be implemented without degradation of the compounds forming the electrolytic solution and, in particular, in the absence of release of gases harmful to man and / or the environment.
    The inventors have also set themselves the goal that this new platinum recovery process can be advantageously implemented to recover, at the cathode and in a single step, the platinum in the form of a metal deposit which is as pure as possible. , and not associated with another metal, for example in the form of an alloy.
    The inventors have further set themselves the goal that this platinum recovery process can be advantageously implemented by limiting energy costs as well as reprocessing costs, such as that of the electrolytic solution, thus making it possible to favorably envisage a transposition on an industrial scale of the corresponding recovery process.
    STATEMENT OF THE INVENTION
    These previously stated aims as well as others are achieved, in the first place, by a process for recovering platinum from a material in which it is contained, this process being of the aforementioned type, that is to say by a method comprising an electrolysis step carried out in an electrolytic solution in which is immersed a system comprising a positive electrode and a negative electrode and connected to a device making it possible to control the potential of one of the two positive and negative electrodes and, more advantageously, to control the potential difference between the positive and negative electrodes. The material is placed on the positive electrode and the electrolytic solution comprises a first ionic liquid LU.
    According to the invention, LU is formed by a first organic cation and a first inorganic anion chosen from the group consisting of the halide anions, dicyanamides N (CN) 2 denoted DCA and thiocyanates SCN, and the electrolytic solution further comprises a second ionic liquid LI2 formed by a second organic cation and a second anion chosen from the group consisting of bis (trifluoromethanesulfonyl) imide anions (CF3SO 2 ) 2 N denoted TFSI, bis (fluorosulfonyl) imide (FSO 2 ) 2 N denoted FSI, trifluoromethanesulfonate or triflate CF3SO3 ', tris (pentafluoroethyl) trifluorophosphate noted FAP and bis (oxalato) borate noted BOB, whereby the platinum is recovered, by electrodeposition thereof, on the negative electrode.
    The inventors have found that the use of an electrolytic solution comprising, no longer a single ionic liquid and a salt in solution such as ZnCI 2 as in publications [1] and [2], AlfNChb or even NH4NO3 described by document [3], or with an inorganic acid such as H 2 PtCl6.6H 2 O also described by document [3], but two ionic liquids LU and LI2 as defined above, makes it possible to recover, in a single step and efficiently and selectively, the platinum contained in the material, this platinum being recovered in the form of metallic platinum and not in the form of an alloy.
    In addition, the use of an electrolytic solution, when it comprises only LU and LI2 ionic liquids, has an undeniable advantage in terms of industrial implementation, not only because of the intrinsic properties of these ionic liquids ( high thermal stability, almost zero vapor pressure and very low flammability), but also taking into account the relatively low temperatures involved, typically between room temperature and 200 ° C, advantageously between room temperature and 150 ° C and, even more advantageously, between room temperature and 100 ° C.
    Furthermore, the platinum recovery process according to the invention makes it possible to optimize the conditions of industrial safety and environmental safety, since no NOx release is observed during its implementation.
    When it is indicated that the electrolytic solution comprises a first ionic liquid LU, it is understood that this electrolytic solution can just as easily comprise a single first ionic liquid LU as a mixture of several (two, three, ...) first ionic liquids READ.
    In the same way, the electrolytic solution can just as well comprise a single second ionic LI2 as a mixture of several (two, three, ...) second ionic liquids LI2.
    In a variant of the invention, the electrolytic solution does not comprise inorganic acid and / or metal salt in solution and this, to avoid the formation of a deposit of the corresponding metal, in addition to that of platinum.
    In another advantageous version of the invention, the electrolytic solution only comprises first (s) and second (s) ionic liquids LU and LI2.
    As previously indicated, an ionic liquid is formed by a cation and an anion. From the nomenclature point of view, the cation is noted in square brackets and indicated first.
    The first ionic liquid LU is formed by a first organic cation and a first inorganic anion chosen from the group consisting of the halide anions, NfCNh and SCN.
    When the first anion of LU is a halide, it is advantageously chosen from the group consisting of Cl, Br, I and is preferably CI.
    The second ionic liquid LI2 is formed by a second organic cation and a second anion, which can be organic or inorganic, this second anion being chosen from the group consisting of TFSI, FSI, CF3SO3 ', FAP and BOB.
    This second anion is advantageously TFSI.
    The first organic cation of the first ionic liquid LU, like the second organic cation of the second ionic liquid LI2, can be chosen from the group consisting of ammonium, imidazolium, pyrrolidinium, phosphonium, sulfonium and piperidinium.
    The first and second organic cations can thus be chosen from the group consisting of a tetraalkylammonium, a / V, / / - dialkylimidazolium, a / V, / / - dialkylpyrrolidinium, a tetraalkylphosphonium, a trialkylsulfonium and an N, Ndialkylpiperidinium.
    In an advantageous variant of the invention, the first organic cation and / or the second organic cation is an imidazolium, such a cation having the advantage of being particularly stable up to a cathodic potential sufficiently high for the electrolytic deposition of platinum . Furthermore, the ionic liquids with imidazolium cation are the least viscous.
    The first organic cation and / or the second organic cation can be a / V, / / - dialkylimidazolium and, preferably, 1-butyl-3-methylimidazolium.
    In a preferred variant of the invention, the first and second organic cations are identical, this choice of first and second identical organic cations making it possible to increase the solubility of the first ionic liquid LU in the second ionic liquid LI2.
    In an advantageous variant of the invention, the electrolytic solution can comprise:
    from 0.5% mol to 50% mol of the first ionic liquid LU, and from 50% mol to 99.5% mol of the second ionic liquid LI2.
    In an advantageous variant of the invention, the molar concentration of the first ionic liquid LU, in the electrolytic solution, is between 0.01 mol / L and 1.5 mol / L, advantageously between 0.02 mol / L and 1 , 0 mol / L, more advantageously between 0.03 mol / L and 0.5 mol / L and, preferably, between 0.05 mol / L and 0.3 mol / L.
    The electrolytic solution can, in addition, comprise an anhydrous drying agent chosen from the group consisting of MgSCL, NazSCL, CaCh, CaSCL, K 2 CO 3 , NaOH, KOH and CaO.
    In an advantageous variant of the invention, the positive electrode comprises a material chosen from the group consisting of a noble metal, indium oxide doped with tin, carbon, stainless steel, tungsten and titanium.
    In an advantageous variant of the invention, the negative electrode comprises a material chosen from the group consisting of stainless steel, carbon, titanium, aluminum, a noble metal, tungsten and an oxide of indium doped with tin.
    In the above, noble metal means one of the following eight metals: gold, silver, rhodium, osmium, palladium, ruthenium, iridium and platinum.
    In a variant of the invention, the electrolysis step is carried out under an argon atmosphere. However, nothing prevents this electrolysis step from being carried out under an uncontrolled atmosphere such as air.
    In an advantageous variant of the invention, the electrolytic solution used also comprises dissolved platinum, the ratio of molar contents of LI1 to platinum [Lll] / [Pt] being advantageously between 5 and 100.
    In a particularly advantageous variant of the invention, this dissolved platinum is introduced, into the electrolytic solution, by prior electrochemical dissolution of platinum, this platinum can either be derived from solid platinum or from a material containing platinum, such as a electrode waste.
    The electrolysis step of the process according to the invention uses a system comprising a positive electrode and a negative electrode, this system being connected to a device making it possible to control the potential of one of the two positive and negative electrodes and, more advantageously, to control the potential difference between the two positive and negative electrodes.
    In a variant of the invention, the device making it possible to control the potential difference between the positive and negative electrodes is a power supply.
    In another variant of the invention, the system further comprises a reference electrode, and the device allowing the control of the potential of one of the two positive and negative electrodes is a potentiostat.
    In an advantageous variant of the invention, the electrolysis step is carried out under alternative potentiostatic control, by the positive electrode then by the negative electrode.
    In another advantageous variant of the invention, the electrolysis step is carried out in a single step, after priming of the solution by dissolution of platinum.
    In a preferred variant of the invention, the material containing the platinum that one seeks to recover is carried to the electrode.
    Such an electrode may in particular come from an electrode membrane assembly of a fuel cell, such as a fuel cell with a PEMFC proton exchange membrane, such a fuel cell possibly being a used battery or corresponding to a manufacturing waste. (discarded battery). In Example 4 which follows, the expression “waste electrode” will be used to designate such an electrode.
    The invention thus relates, secondly, to a process for recovering platinum contained in the electrodes of a fuel cell, this fuel cell comprising membrane electrode assemblies and bipolar plates.
    According to the invention, this method comprises the following successive steps:
    (a) a step of separating the membrane electrode assemblies and the bipolar plates, (b) a step of separating the membrane and the electrodes of each membrane electrode assembly separated in step (a), and (c) a step of recovery of the platinum contained in these electrodes by the implementation of the platinum recovery process as defined above, the advantageous characteristics of this process being able to be taken alone or in combination.
    In other words, the process for recovering platinum contained in the electrodes of such a fuel cell comprises successively and in this order:
    (a) a step of separating the electrode membrane assemblies and the bipolar plates, (b) a step of separating the membrane and the electrodes of each membrane electrode assembly separated in step (a), and (c) a step d electrolysis carried out in an electrolytic solution in which a system comprising a positive electrode and a negative electrode is immersed and connected to a device making it possible to control the potential of one of the two positive and negative electrodes, advantageously the potential difference between the electrodes positive and negative, each of the electrodes separated in step (b) and containing platinum being disposed on the positive electrode and the electrolytic solution comprising a first ionic liquid LU formed by a first organic cation and a first inorganic anion chosen from group consisting of halide anions, dicyanamides and thiocyanates, and a second ionic liquid LI2 formed by a second organic cation and a second anion chosen from the group consisting of the TFSI, FSI, CF3SO3 ', FAP and BOB anions, whereby the platinum contained in each of the electrodes separated by l is recovered from the negative electrode 'step (b).
    In an advantageous variant of the invention, the positive electrode consists of the material containing the platinum that one seeks to recover.
    In a variant of the invention, the positive electrode consists of each of the electrodes of the fuel cell separated in step (b).
    In a variant of the invention, the fuel cell is a fuel cell with a PEMFC proton exchange membrane, preferably a spent cell or a discarded cell.
    Other characteristics and advantages of the invention will appear better on reading the additional description which follows, which relates to recovery tests, by electrochemical dissolution and electrodeposition, of platinum from a platinum anode by means of reference electrolytic solutions (SI to S3) and electrolytic solutions according to the invention (S4 and S5), as well as from an electrode waste by means of electrolytic solutions according to the invention (S4, S4 ', S5 and and S5').
    It is specified that this detailed description, which refers in particular to FIGS. 1 to 16B as appended, is given only by way of illustration of the subject of the invention and does not in any way constitute a limitation of this object.
    In particular, the platinum recovery process described above and detailed below makes it possible to obtain at least the electrochemical dissolution of the platinum in the electrolytic solution.
    BRIEF DESCRIPTION OF THE DRAWINGS
    Figure 1 illustrates the curve obtained in anodic linear voltammetry translating the evolution of the intensity (noted I and expressed in mA) according to the potential (noted E and expressed in V compared to the couple Ag + I / Ag, noted VvsAg + l / Ag) applied to the system comprising the platinum anode in the electrolytic solution S2.
    FIG. 2 illustrates the chronoamperometry curve translating the evolution of the intensity I (in mA) as a function of time (noted t and expressed in h) when the system comprising the platinum anode in the electrolytic solution S2 is subjected to overvoltage.
    Figure 3 illustrates the curve obtained in cyclic voltammetry translating the evolution of the intensity I (in mA) as a function of the potential E (in Vvs Ag + I / Ag) applied to the system comprising the glassy carbon cathode in the electrolytic solution S2 '.
    FIG. 4 illustrates the curve obtained in anodic linear voltammetry translating the evolution of the intensity I (in mA) as a function of the potential E (in VvsAg + l / Ag) applied to the system comprising the platinum anode in the electrolytic solution S4, under controlled atmosphere (argon).
    FIG. 5 illustrates the chronoamperometry curve translating the evolution of the intensity I (in mA) as a function of time t (in h) when the system comprising the platinum anode in the electrolytic solution S4 is subjected to an overvoltage, under a controlled atmosphere (argon).
    FIGS. 6A correspond to SEM pictures of the deposit obtained in Example 2, while FIG. 6B corresponds to the EDX analysis of this deposit.
    FIG. 7 illustrates the curve obtained in anodic linear voltammetry translating the evolution of the intensity I (in mA) as a function of the potential E (in VvsAg + l / Ag) applied to the system comprising the platinum anode in the electrolytic solution S5, in an uncontrolled atmosphere (air).
    FIG. 8 illustrates the chronoamperometry curve translating the change in intensity I (in mA) as a function of time t (in h) when the system comprising the platinum anode in the electrolytic solution S5 is subjected to an overvoltage, in an uncontrolled atmosphere (air).
    FIG. 9 illustrates the curve obtained in cathodic linear voltammetry translating the evolution of the current density J (in mA.cm 2 ) as a function of the potential E (in VvsAg + l / Ag) applied to the system comprising the glassy carbon cathode in S5 electrolytic solution, in an uncontrolled atmosphere (air).
    FIGS. 10A correspond to SEM pictures of the deposit obtained in Example 3, while FIG. 10B corresponds to the EDX analysis of this deposit.
    FIG. 11 illustrates the curve obtained in cathodic linear voltammetry translating the evolution of the current density J (in mA.cm 2 ) as a function of the potential E (in VvsAg + l / Ag) applied to the system comprising the glassy carbon cathode in the electrolytic solution S4 ', under a controlled atmosphere (argon).
    FIGS. 12A and 12B correspond to SEM shots and EDX analysis of the electrode waste at the end of the implementation of Example 4.1.
    FIGS. 13A and 13B correspond to SEM and EDX analysis of the glassy carbon cathode at the end of the implementation of Example 4.1.
    FIG. 14 illustrates the curve obtained in cathodic linear voltammetry translating the evolution of the intensity (in mA) as a function of the potential E (in VvsAg + l / Ag) applied to the system comprising the glassy carbon cathode in the electrolytic solution S5 ', in an uncontrolled atmosphere (air).
    FIGS. 15A and 15B correspond to SEM and EDX analysis of the anode constituted by the electrode waste at the end of the implementation of Example 4.2.
    FIGS. 16A and 16B correspond to SEM and EDX analysis of the glassy carbon cathode at the end of the implementation of Example 4.2.
    DETAILED PRESENTATION OF PARTICULAR EMBODIMENTS
    EXAMPLE 1 Electrolytic solutions constituted by an ionic liquid LU
    1.1 Study of the electrochemical dissolution of a massive platinum electrode in these electrolytic solutions
    The electrolytic device used in this study consists of a cell comprising three electrodes:
    - a glassy carbon cathode as a counter electrode,
    - a solid platinum anode worn as a working electrode, and
    - an Ag + I / Ag reference electrode produced by balancing a silver wire with a solution of 1butyl-3-methylimidazolium trifluoromethanesulfonate [BMIMHSO3CF3], also noted [BMIM] [OTf], containing 10 mmol / L of AgOTf silver triflate.
    The following three electrolytic solutions, denoted SI to S3, each consisting of an imidazolium chloride, were evaluated:
    : 1-methylimidazolium chloride ([MIM] [CI]),: l-butyl-3-methylimidazolium chloride ([BMIM] [CI]), and: l-hexyl-3-methylimidazolium chloride ([HMIM] [ THIS]).
    The electrochemical dissolution tests were carried out under an inert argon atmosphere, using a glove box and at a working temperature of 100 ° C., two of the ionic liquids studied having melting temperatures above the temperature ambient. The temperature is kept constant at 100 ° C. by heating using a dry bath.
    Electrochemical dissolution study protocol
    The protocol used in the study of the electrochemical dissolution of the platinum anode will be described in relation to the electrolytic solution S2 ([BMIM] [CI]).
    Beforehand, a voltammetric study of the system was carried out in order to determine the oxidation potential of platinum.
    Referring to FIG. 1 illustrating the evolution of the intensity curve I as a function of the potential E, at a scanning speed Vb = 20 mV / s, of the platinum in the electrolytic solution S2 at a temperature of 100 ° C., we observes the appearance of an oxidation current from 0.8 V vs Ag + I / Ag, current which corresponds to the oxidation of chlorides as well as to the oxidation of platinum according to the applied overvoltage.
    The electrochemical dissolution of the platinum anode in the electrolytic solution S2 was therefore carried out, under potentiostatic control, that is to say by applying a fixed potential, located above 0.8 V vs Ag + I / Ag, in this case under the application of a 1.4 V overvoltage vs Ag + I / Ag.
    FIG. 2 illustrates the chronoamperogram as obtained during the electrochemical dissolution of the platinum anode in the electrolytic solution S2, at a temperature of 100 ° C., the quantity of electricity Q supplied being 30 C.
    At the end of the chronoamperometry, the platinum anode is extracted from the electrolytic solution S2 'thus obtained, then weighed. As for the electrolytic solution S2 ′, it is analyzed by Atomic Absorption Spectrometry (abbreviated SAA), so as to determine the quantity of platinum which has been dissolved.
    The amount of platinum dosed by SAA is in agreement with the loss of mass of the anode and corresponds to 11 mg. The dissolution rate of the platinum is also determined and given in table 1 below.
    It is specified that a dissolution test, carried out by chronopotentiometry with the same system but by applying, no longer a fixed overvoltage but a fixed intensity, gives a result similar to that obtained by chronoamperometry.
    Results of the electrochemical dissolution study
    The protocol which has just been described has been reproduced with the two other electrolytic solutions SI and S3.
    The operating conditions and results of the electrochemical dissolution tests in each of the electrolytic solutions SI to S3 are collated in table 1 below.
    Solution T 1 applied E medium Q Pt Speed of electrolytic ro (my) (V vs Ag + I / Ag) (VS) dissolved dissolution (mg.h _1 .cm 2 ) IF 100 6.8 1.02 30 Yes 19.3 S2 100 6.8 1.4 30 Yes 16.86 S3 150 6.8 1.14 30 Yes 28.6
    Table 1
    It is specified that the dissolution of the platinum anode in the electrolytic solution S3 was carried out, not at a temperature of 100 ° C, but at a temperature of 150 ° C, due to the formation of a blocking film on the anode observed for temperatures between 80 ° C and 100 ° C.
    As is clear from Table 1 above, the electrochemical dissolution, or anodic dissolution, of the platinum in each of the three electrolytic solutions SI to S3 is clearly observed, the working temperature having to be adapted to the ionic liquid used, to avoid the formation a blocking film on the anode.
    1.2 Study of the electrodeposition of platinum dissolved in the electrolytic solution S2
    The platinum electrodeposition study was carried out with an electrolytic solution S2 'constituted by the ionic liquid [BMIM] [Cl] containing 7.5 mmol / L of dissolved platinum, this quantity of dissolved platinum being able in particular to be introduced by dissolution electrochemical prior to solid platinum or an electrode waste containing platinum.
    The electrolytic device used in this second study is of the same type as that used in Chapter 1.1, with the exception of the glassy carbon electrode and the solid platinum electrode, which are respectively used as working electrode (cathode) and counter electrode (anode).
    Beforehand, and as previously for the electrochemical dissolution study, a voltammetric study was carried out in order to determine the potential to be applied to carry out the platinum deposition tests.
    FIG. 3 illustrates the curve thus obtained and which shows the evolution of the intensity curve I as a function of the potential E, at a scanning speed Vb = 20 mV / s, of the system with the electrolytic solution S2 'at a temperature of 100 ° C.
    In view of the data in FIG. 3, the electrodeposition tests were carried out by fixing a potential situated in the range from -1 V vs Ag + I / Ag to -2 V vs Ag + I / Ag.
    However, in this range, no platinum deposit has been obtained.
    It is therefore impossible to obtain, on the glassy carbon cathode, the electrodeposition of the platinum dissolved in the electrolytic solution S2 'which comprises only one ionic liquid, in this case [BMIM] [Cl].
    This same observation was obtained with the electrodeposition tests from an electrolytic solution SI 'constituted by the ionic liquid [MIM] [CI] containing 7.5 mmol / L of dissolved platinum or from an electrolytic solution S3 ′ constituted by the ionic liquid [H Ml M] [Cl] containing 7.5 mmol / L of dissolved platinum.
    The non-feasibility of an electrolytic deposition of platinum is explained by the formation of a stable chlorine complex which cannot be reduced in the electroactivity field of ionic liquids of electrolytic solutions SI 'to S3'.
    In conclusion, this example 1 shows that, if it is possible to dissolve platinum electrochemically in an electrolytic solution comprising only one ionic liquid, it is, however, impossible to deposit platinum by this same electrochemical route dissolved in this single ionic liquid, due to the formation of a complex too stable to be able to be reduced.
    EXAMPLE 2 S4 electrolytic solution according to the invention
    The recovery tests, by electrochemical dissolution and electrodeposition, of the platinum were carried out using the same electrolytic device as that used in example 1, the solid platinum being placed in working electrode (anode), the counter-electrode (cathode ) being made of vitreous carbon and the reference electrode being an Ag + I / Ag electrode.
    The tests were carried out using a glove box, at a working temperature of 100 ° C. and under a controlled atmosphere, in this case an inert atmosphere of argon, with water and oxygen contents. less than 0.5 ppm.
    The electrolytic solution tested, denoted S4, was prepared by dissolving a first ionic liquid LU, in this case l-butyl-3methylimidazolium chloride ([BMIM] [CI]) in a second ionic liquid LI2, in l 'bis-trifluoromethanesulfonyl) imide species of l-butyl-3-methylimidazolium ([BMIM] [TFSI]), the molar concentration of [BMIM] [CI] being 0.1 mol / L in the mixture comprising LU and LI2.
    It is specified that this mixture [BMIM] [TFSI] + [BMIM] [CI] (0.1 mol / L) is liquid at room temperature.
    A voltammetric study of the system using the electrolytic solution S4 was carried out in order to determine the potential to be applied to achieve the electrochemical dissolution of platinum.
    Referring to FIG. 4 illustrating the evolution of the intensity curve I as a function of the potential E, at a scanning speed Vb = 20 mV / s, of the platinum in the electrolytic solution S4, the appearance of a oxidation current from
    1.2 V vs Ag + I / Ag, current which corresponds to the oxidation of chlorides and platinum. The signal observed at 3 V vs Ag + I / Ag corresponds, in turn, to the oxidation of the TFSI anion.
    The electrochemical dissolution test of the platinum anode in the electrolytic solution S4, at a temperature of 100 ° C., was therefore carried out by applying a potential of 1.2 V vs Ag + I / Ag.
    FIG. 5 illustrates the chronoamperogram thus obtained, the quantity of electricity Q supplied being 30 C.
    The platinum electrode is then extracted from the electrolytic solution S4, then weighed so as to determine its loss in mass. The amount of dissolved platinum is 11.6 mg. The operating conditions as well as the dissolution rate are recorded in table 2 below.
    Electrolytic solution T(° C) E applied (V vs Ag + I / Ag) Pt dissolved Dissolution rate (mg.hùcm 2 ) S4 100 1.2 Yes 1.47
    Table 2
    It is observed, moreover, obtaining a deposit with the vitreous carbon counter-electrode. This deposit was the subject of pictures using a scanning electron microscope (SEM) as well as analyzes using an energy dispersive analysis probe (in English, energy dispersive X-ray spectrometry and abbreviated EDX) to determine its chemical composition. The results of these SEM photographs and EDX analyzes, respectively presented in FIGS. 6A and 6B, show that this deposit consists mainly of platinum, with some traces of carbon, sulfur and fluorine coming from the fluorinated anion TFSI of the ionic liquid [ BMIM] [TFSI],
    It is therefore possible to carry out, simultaneously, in a unitary electrolytic device, the electrochemical dissolution as well as the electrodeposition of platinum, and therefore to recover platinum, with an electrolytic solution comprising a mixture of two ionic liquids [BMIM] [TFSI] + [BMIM] [CI] (0.1 mol / L) under an inert atmosphere.
    Platinum was also successfully recovered by simultaneous electrochemical dissolution and electrodeposition of platinum, under the same operating conditions, with the following electrolytic solutions:
    - [BMIM] [TFSI] + [BMIM] [Cl] (0.05 mol / L),
    - [BMIM] [TFSI] + [HMIM] [CI] (0.1 mol / L), and
    - [BMIM] [TFSI] + [BMIM] [Br] (0.1 mol / L).
    EXAMPLE 3 S5 electrolytic solution according to the invention
    The recovery tests, by electrochemical dissolution and electrodeposition, of the platinum were carried out at a working temperature of 100 ° C., under an uncontrolled atmosphere, in this case air, using the same electrolytic device as that used in Example 1, the solid platinum being placed as a working electrode (anode), the counter electrode (cathode) being made of vitreous carbon and the reference electrode being an Ag + I / Ag electrode.
    The electrolytic solution tested, denoted S5, comprises a first ionic liquid LU, in this case [BMIM] [CI], and a second ionic liquid LI2, in this case [BMIM] [TFSI], the molar concentration of [BMIM ] [CI] being 0.05 mol / L in the mixture comprising LU and LI2.
    The voltammetric study was previously carried out in order to determine the potential to be fixed for carrying out the electrochemical dissolution of platinum at a temperature of 100 ° C. The voltammogram (Vb = 20 mV / s) obtained is shown in Figure 7.
    Simultaneous electrochemical dissolution and electrodeposition were carried out by priming the solution by first dissolving the anode containing platinum in potentiostatic mode at 1.2 V vs Ag + I / Ag (see FIG. 8), then by performing the electrodeposition / electrodissolution step simultaneously, by potentiostatic control of the cathode at -0.32 V vs Ag + I / Ag (see FIG. 9).
    After having consumed 30 ° C., a mass loss of 11.5 mg of platinum is measured on the anode, corresponding to a dissolution rate of 1.6 mg.h Lcm ' 2 .
    We also observe the presence of a deposit on the glassy carbon electrode. This deposit was analyzed by MEB and EDX to determine its chemical composition.
    The results of these analyzes, respectively presented in FIGS. 10A and 10B, show that this deposit consists mainly of platinum.
    This example 3 shows that it is possible to recover platinum, by simultaneous electrochemical dissolution and electrodeposition thereof, under an uncontrolled atmosphere such as air, using an adequate concentration of first ionic liquid, here [BMIM] [ Cl], and by initiating the electrochemical dissolution of the platinum by alternating the potential control.
    The alternation of the potential control makes it possible to initiate the electrochemical dissolution (which results in the presence of dissolved platinum in the electrolytic solution) and to initiate a deposition of platinum (by controlling the potential of the cathode in a second step) .
    EXAMPLE 4 Recovery tests from an electrode waste from AME
    The following tests were carried out using electrode waste from an electrode membrane assembly (AME). This electrode waste, with an area of 1.44 cm 2 , is composed of platinum nanoparticles supported on carbon, the charge of platinum being 75 pg / cm 2 .
    This electrode waste being electrically conductive, it is directly carried as an anode of the electrolytic device of the same type as that used in chapter 1.1. The cathode is, in turn, formed by a glassy carbon electrode and the reference electrode is an Ag + I / Ag electrode.
    4.1 Recovery test with electrolytic solution S4 '
    The test is carried out under a controlled argon atmosphere at a temperature of 100 ° C. with the electrolytic solution S4 ′ constituted by the mixture [BMIM] [TFSI] + [BMIM] [Cl] (0.1 mol / L) + 7.5 mmol / L of dissolved platinum, this dissolved platinum being introduced by prior electrochemical dissolution of solid platinum.
    The voltammetric study, which was previously carried out to determine the potential to be applied to obtain the electrochemical dissolution of the platinum nanoparticles, indicates that the deposition potential is at -0.4 V vs Ag + I / Ag (see Figure 11, Vb = 20 mV / s).
    The test was therefore carried out by fixing the potential of the glassy carbon cathode at -0.5 V vs Ag + I / Ag. The amount of coulombs applied is 5 C.
    At the end of the test, the anode and the cathode were analyzed by SEM and EDX in order to control the electrochemical dissolution of the platinum at the anode and the electrodeposition of platinum on the glassy carbon cathode.
    With reference to FIGS. 12A and 12B, it is observed that the SEM and EDX analyzes of the electrode waste originating from ΙΆΜΕ indicate a significant electrochemical dissolution of the platinum on the surface of this electrode with a few residual particles.
    With reference to FIGS. 13A and 13B, the SEM and EDX analyzes of the glassy carbon cathode show the presence of a platinum deposit on this electrode, with some traces of copper and sulfur.
    It is therefore possible to obtain the electrochemical dissolution as well as the electrodeposition of platinum under a controlled atmosphere, simultaneously, in an electrolytic solution according to the invention, by initiating the electrochemical dissolution and the electrodeposition by the introduction of small quantities of platinum. dissolved in the electrolytic solution.
    4.2 Recovery test with electrolytic solution S5 '
    The test is carried out in an uncontrolled atmosphere (air) at a temperature of 100 ° C. with the electrolytic solution S5 ′ constituted by the mixture [BMIM] [TFSI] + [BMIM] [CI] (0.05 mol / L) + 7.5 mmol / L of dissolved platinum, introduced by prior electrochemical dissolution of solid platinum.
    The voltammetric study, which was previously carried out to determine the potential to be applied to obtain the electrochemical dissolution of the platinum nanoparticles, indicates that the deposition potential is at -0.15 V vs Ag + I / Ag (see Figure 14, Vb = 20 mV / s).
    The test was therefore carried out by fixing the potential of the glassy carbon cathode at -0.5 V vs Ag + I / Ag. The amount of coulombs applied is 5 C.
    At the end of the test, the anode and the cathode were analyzed by MEB and EDX in order to control the electrochemical dissolution of the platinum on the anode and the electrodeposition of platinum on the glassy carbon cathode.
    With reference to FIGS. 15A and 15B, it is observed that the SEM and EDX analyzes of the electrode waste from ΙΆΜΕ indicate a total electrochemical dissolution of the platinum on the surface of the waste.
    With reference to FIGS. 16A and 16B, the SEM and EDX analyzes of the vitreous carbon cathode show the presence of a platinum deposit on this electrode, with some traces of sulfur coming from the anion of the second ionic liquid [BMIM] [TFSI],
    It is therefore possible to obtain the electrochemical dissolution as well as the platinum electrodeposition simultaneously, and therefore the recovery of platinum, in an electrolytic solution according to the invention and this, in an uncontrolled atmosphere such as air, by initiating these dissolution. electrochemical and electroplating, by the introduction of small quantities of platinum dissolved in the electrolytic solution.
    BIBLIOGRAPHY [1] J.-F. Huang et al., Angew. Chem. Int. Ed., 2012, 51, pages 1684-1688 [2] C. Deferm et al., J. Appl. Electrochem., 2013, 43, pages 797-804 [3] WO 2006/074523 Al
    权利要求:
    Claims (19)
    [1" id="c-fr-0001]
    1. A method of recovering platinum from a material in which it is contained, this method comprising an electrolysis step carried out in an electrolytic solution in which is immersed a system comprising a positive electrode and a negative electrode and connected to a device for controlling the potential of one of the two positive and negative electrodes, advantageously the potential difference between the positive and negative electrodes, the material being placed on the positive electrode and the electrolytic solution comprising a first ionic liquid LU, characterized in that LI1 is formed by a first organic cation and a first inorganic anion chosen from the group consisting of halide, dicyanamide and thiocyanate anions, and in that the electrolytic solution further comprises a second ionic liquid LI2 formed by a second organic cation and a second anion chosen from the group consisting of the anions TFSI, FSI, CF3SO3, FAP and BOB, whereby the platinum is recovered on the negative electrode.
    [2" id="c-fr-0002]
    2. The method of claim 1, wherein the system further comprises a reference electrode, and the device for controlling the potential of one of the two positive and negative electrodes is a potentiostat.
    [3" id="c-fr-0003]
    3. The method of claim 1, wherein the device for controlling the potential difference between the positive and negative electrodes is a power supply.
    [4" id="c-fr-0004]
    4. Method according to any one of claims 1 to 3, wherein the first anion is chosen from the group consisting of CI, Br, I and is preferably CI.
    [5" id="c-fr-0005]
    5. Method according to any one of claims 1 to 4, wherein the second anion is TFSI.
    [6" id="c-fr-0006]
    6. Method according to any one of claims 1 to 5, in which the first and second organic cations are chosen from the group consisting of ammonium, imidazolium, pyrrolidinium, phosphonium, sulfonium and piperidinium.
    [7" id="c-fr-0007]
    7. The method of claim 6, wherein the first organic cation and / or the second organic cation is an imidazolium, advantageously a / V, / V-dialkylimidazolium and, preferably, l-butyl-3-methylimidazolium.
    [8" id="c-fr-0008]
    8. Method according to any one of claims 1 to 7, wherein the first and second organic cations are identical.
    [9" id="c-fr-0009]
    9. Method according to any one of claims 1 to 8, in which the electrolytic solution comprises:
    from 0.5% mol to 50% mol of the first ionic liquid LU, and from 50% mol to 99.5% mol of the second ionic liquid LI2.
    [10" id="c-fr-0010]
    10. Method according to any one of claims 1 to 9, in which the molar concentration of the first ionic liquid, in the electrolytic solution, is between 0.01 mol / L and 1.5 mol / L, advantageously between 0, 02 mol / L and 1.0 mol / L, more advantageously between 0.03 mol / L and 0.5 mol / L and, preferably between 0.05 mol / L and 0.3 mol / L.
    [11" id="c-fr-0011]
    11. Method according to any one of claims 1 to 10, in which the electrolytic solution further comprises an anhydrous drying agent chosen from the group consisting of MgSCU, Na 2 SO4, CaCI 2 , CaSCU, K 2 CC> 3 , NaOH, KOH and CaO.
    [12" id="c-fr-0012]
    12. Method according to any one of claims 1 to 11, in which the positive electrode comprises a material chosen from the group consisting of a noble metal, indium oxide doped with tin, carbon, stainless steel, tungsten and titanium.
    [13" id="c-fr-0013]
    13. Method according to any one of claims 1 to 12, in which the negative electrode comprises a material chosen from the group consisting of stainless steel, carbon, titanium, aluminum, a noble metal, tungsten and an indium oxide doped with tin.
    [14" id="c-fr-0014]
    14. Method according to any one of claims 1 to 13, wherein the electrolysis step is carried out under an argon atmosphere.
    [15" id="c-fr-0015]
    15. Method according to any one of claims 1 to 14, in which the electrolytic solution further comprises dissolved platinum, the ratio of molar contents of LU to platinum [LU] / [Pt] being advantageously between 5 and 100.
    [16" id="c-fr-0016]
    16. Method according to any one of claims 1 to 15, in which the electrolysis step is carried out:
    - either under an alternative potentiostatic control, by the positive electrode then by the negative electrode,
    - either in a single step, after priming of the solution by dissolution of platinum.
    [17" id="c-fr-0017]
    17. Method according to any one of claims 1 to 16, in which the platinum-containing material consists of an electrode waste, this electrode waste being able to come from a fuel cell such as a fuel cell. with proton exchange membrane.
    [18" id="c-fr-0018]
    18. Method for recovering platinum contained in fuel cell electrodes comprising membrane electrode assemblies and bipolar plates, this method comprising the following successive steps:
    (a) a step of separating the membrane electrode assemblies and the
    5 bipolar plates, (b) a step of separating the membrane and the electrodes of each membrane electrode assembly separated in step (a), and (c) a step of recovering the platinum contained in the electrodes by the implementation of the platinum recovery process according to one
    10 any of claims 1 to 17.
    [19" id="c-fr-0019]
    19. The method of claim 18, wherein the fuel cell is a PEMFC proton exchange membrane fuel cell, preferably worn or scrapped.
    S.60194
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    同族专利:
    公开号 | 公开日
    EP3263744B1|2019-05-15|
    FR3053364B1|2018-08-10|
    EP3263744A1|2018-01-03|
    引用文献:
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    WO2001013379A1|1999-08-18|2001-02-22|British Nuclear Fuels Plc|Process for separating metals|
    WO2006074523A1|2005-01-13|2006-07-20|Commonwealth Scientific And Industrial Research Organisation|Recovery of metals|
    JP2011122242A|2009-11-16|2011-06-23|Yokohama National Univ|Method for recovering platinum group element and/or rare earth element, and device for recovering the platinum group element and the rare earth element|
    WO2016054265A1|2014-09-30|2016-04-07|The Board Of Regents Of The Nevada System Of Higher Education On Behalf Of The University Of Nevada|Processes for recovering rare earth elements|
    KR101629918B1|2014-12-04|2016-06-13|한국원자력연구원|Electrolytic apparatus for electro-refining and recovery of platinum metals, and method thereof|
    FR3099492B1|2019-08-02|2021-09-03|Commissariat Energie Atomique|PROCESS FOR RECOVERING RHODIUM BY ELECTROCHEMICAL METHOD|
    FR3099493B1|2019-08-02|2021-09-10|Commissariat Energie Atomique|ELECTROPOLISHING PROCESS OF RHODIUM-COATED PARTS BY GREEN CHEMISTRY|
    FR3102679A1|2019-10-31|2021-05-07|Commissariat A L'energie Atomique Et Aux Energies Alternatives|PROCESS FOR RECOVERING PLATINOID PARTICLES CONTAINED IN AN ELECTRICALLY INSULATING SUPPORT|
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    FR1656293A|FR3053364B1|2016-07-01|2016-07-01|PROCESS FOR THE RECOVERY OF PLATINUM BY ELECTROCHEMICAL MEANS FROM A MATERIAL IN WHICH IT IS CONTENT|FR1656293A| FR3053364B1|2016-07-01|2016-07-01|PROCESS FOR THE RECOVERY OF PLATINUM BY ELECTROCHEMICAL MEANS FROM A MATERIAL IN WHICH IT IS CONTENT|
    EP17179196.5A| EP3263744B1|2016-07-01|2017-06-30|Process for the recovery of platinum, electrochemically, from a material which contains same|
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