Abstract
A method for recovering gold, silver, and/or platinum from components of a fuel cell stack of a fuel cell or electrolyzer includes treating the components with an aqueous electrolyte solution and with at least one gaseous oxidant in the fuel cell or the electrolyzer in an oxidation step. In a reduction step, the components are treated with a flow of an aqueous electrolyte solution and with at least one gaseous reductant in the fuel cell or the electrolyzer. A device by which the method can be carried out has a reservoir for the electrolyte solution, a line connected to an outlet opening of the reservoir, the line having a pump, an anode inlet connection connected to an anode inlet, and a cathode inlet connection connected to a cathode inlet. An oxidant-introducer introduces a gaseous oxidant into the line. A reductant-introducer introduces a gaseous reductant and/or inert gas into the line.
Claims
1. A process for recovering at least one of gold, silver, and platinum metal from constituents of a fuel cell stack of a fuel cell or of an electrolyzer, the method comprising: oxidizing the constituents by treating the constituents with a first stream of a first aqueous electrolyte solution and with at least one gaseous oxidant in the fuel cell or the electrolyzer; and reducing the constituents by treating the constituents with a second stream of a second aqueous electrolyte solution and with at least one gaseous reducing agent in the fuel cell or the electrolyzer.
2. The process as claimed in claim 1, further comprising: flushing the constituents between the oxidizing and the reducing by treating the constituents with at least one inert gas.
3. The process as claimed in claim 2, wherein the first and second aqueous electrolyte solutions are the same electrolyte solution, and the flushing includes using the same electrolyte solution.
4. The process as claimed in claim 1, wherein the first and second electrolyte solutions are conveyed from at least one stock vessel to the constituents and, after contact with the constituents, the first and second electrolyte solutions are collected in a collection vessel.
5. The process as claimed in claim 1, wherein the first and second electrolyte solutions are conveyed in a circuit in which the first and second electrolyte solutions are brought into contact with the constituents a number of times.
6. The process as claimed in claim 1, wherein the first and second electrolyte solutions include at least one alkali metal chloride, alkali metal bromide, and/or alkali metal iodide.
7. The process as claimed in claim 1, further comprising: a first part, including the oxidizing and reducing, in which the constituents are treated with the first and second electrolyte solutions having a pH of greater than 7; and a second part in which the constituents are treated with a third electrolyte solution having a pH of less than 7.
8. An apparatus for recovering at least one of gold, silver, and platinum metal from constituents of a fuel cell stack of a fuel cell or electrolyzer, comprising: at least one stock vessel for an electrolyte solution, the at least one stock vessel including an outlet opening; a first conduit which is connected to the outlet opening, the first conduit including an anode inlet connection connected to an anode inlet of the fuel cell or electrolyzer and a cathode inlet connection connected to a cathode inlet of the fuel cell or electrolyzer; at least one oxidant feed conduit configured for introducing at least one gaseous oxidant into the first conduit; at least one reducing agent feed conduit configured for introducing at least one gaseous reducing agent and/or inert gas into the first conduit; and at least one first pump arranged in the first conduit.
9. The apparatus as claimed in claim 8, further comprising: a second conduit including an anode outlet connection and a cathode outlet connection for the fuel cell; a collection vessel for the electrolyte solution, the collection vessel connected to the second conduit; and at least one second pump arranged in the second conduit.
10. The apparatus as claimed in claim 8, further comprising: a second conduit including an anode outlet connection connected to an anode outlet of the fuel cell or electrolyzer and a cathode outlet connection connected to a cathode outlet of the fuel cell or electrolyzer and is connected to the first conduit upstream of the at least one oxidant feed conduit and the at least one reducing agent feed conduit.
11. The apparatus as claimed in claim 8, further comprising: a second conduit including an anode outlet connection connected to an anode outlet of the fuel cell or electrolyzer and a cathode outlet connection connected to a cathode outlet of the fuel cell or electrolyzer, the cathode outlet connection connected to an inlet opening of the stock vessel.
12. The apparatus as claimed in claim 8, further comprising: an electrochemical ozonizer having an ozone outlet and a hydrogen outlet, wherein the ozone outlet functions as the at least one oxidant feed conduit and the hydrogen outlet functions as the at least one reducing agent feed conduit.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0022] Working examples of the invention are presented in the drawings and will be described in more detail in the following description.
[0023] FIG. 1 schematically shows an apparatus for recovering gold and/or silver and/or at least one platinum metal as per one working example of the invention.
[0024] FIG. 2 schematically shows an apparatus for recovering gold and/or silver and/or at least one platinum metal as per another working example of the invention.
[0025] FIG. 3 schematically shows an apparatus for recovering gold and/or silver and/or at least one platinum metal as per still another working example of the invention.
[0026] FIG. 4 schematically shows an apparatus for recovering gold and/or silver and/or at least one platinum metal as per still another working example of the invention.
[0027] FIG. 5 schematically shows an apparatus for recovering gold and/or silver and/or at least one platinum metal as per still another working example of the invention.
[0028] FIG. 6 schematically shows an apparatus for recovering gold and/or silver and/or at least one platinum metal as per still another working example of the invention.
WORKING EXAMPLES OF THE INVENTION
[0029] FIG. 1 depicts a fuel cell 10 which is connected to an apparatus as per a first working example of the invention. The fuel cell 10 contains a fuel cell stack 11. This contains ruthenium and platinum as catalyst materials on carbon as support material. An aqueous electrolyte solution containing 0.1 M NaOH and 3 M NaCl is kept in stock in a stock vessel 20. This electrolyte solution has a pH of 13. The stock vessel 20 is connected via an outlet opening 21 to a first conduit 30. The first conduit 30 branches to form an anode inlet connection 31 and a cathode inlet connection 32 at the fuel cell 10. Before the branching point, an oxidant feed conduit 33 and a reducing agent feed conduit 34, which are each configured as a Venturi nozzle, are arranged on the first conduit 30. Downstream of the oxidant feed conduit 33 and the reducing agent feed conduit 34, a pump 35 is arranged in the first conduit 30 upstream of the branching point in order to convey the electrolyte solution through the first conduit 30. A second conduit 40 is connected to an anode outlet connection 41 and a cathode outlet connection 42 on the fuel cell 10. Two subsections of this second conduit 40, which go out from the fuel cell 10, combine to form a joint conduit in which a second pump 43 is arranged. This second pump 43 conveys the electrolyte solution introduced by means of the first pump 35 into the fuel cell 10 out from the fuel cell again and conveys it into a collection vessel 50. The oxidant feed conduit 33 is connected to an ozonizer 61 which produces a mixture of oxygen and ozone by means of the corona effect. The reducing agent feed conduit 34 is connected to a gas conduit 62 through which hydrogen, carbon monoxide, nitrogen or mixtures of these gases can be introduced as desired. The collection vessel 50 is connected via further conduits to an ozone decomposer 63 in order to decompose ozone which has gone into the stock vessel 50 and exits from the latter.
[0030] In one working example of the process of the invention, electrolyte solution is introduced into the fuel cell 10 and is admixed with ozone by means of the oxidant feed conduit 33 in a first oxidation step. Here, surface oxidation of platinum and ruthenium takes place in the fuel cell stack 11. Since chloro complexes of platinum are not stable in aqueous solution above a pH of 7, no platinum goes into solution. However, transient dissolution of ruthenium takes place. After a compact oxide layer has been formed on the surface of the metals, the dissolution stops. The introduction of the electrolyte solution is now continued in a flushing step, but this electrolyte solution is no longer admixed with ozone but instead is admixed with nitrogen by means of the reducing agent feed conduit 34. After the unreacted ozone has been flushed from the fuel cell 10 by means of this inert gas, the stream of electrolyte solution is admixed with hydrogen via the reducing agent feed conduit 34 in a reduction step. Here, the oxide layer in the fuel cell stack 11 is reduced, with further ruthenium going into solution. As soon as all oxides have been reduced, a further flushing step in which nitrogen is fed into the stream of the electrolyte solution is carried out in order to remove unreacted hydrogen from the fuel cell 10. The reaction steps commencing with the oxidation step are then repeated until all of the ruthenium has been dissolved. A measuring unit, which is not shown, is arranged in the second conduit 40 or in the collection vessel 50 so as to be able to monitor the concentration of ruthenium complexes in the stream of electrolyte solution in order to control the change between the individual reaction steps. After dissolution of all of the ruthenium, the ruthenium solution collected in the collection vessel 50 is taken off from the latter.
[0031] The electrolyte solution in the stock vessel 20 is now replaced by an aqueous solution of 0.3 M HCl and 3 M NaCl. This has a pH of about 0.5. The sequence of oxidation step, flushing step, reduction step and renewed flushing step carried out previously using the first electrolyte solution is now repeated using this new electrolyte solution. However, the electrolyte solution is admixed not with pure hydrogen but with a mixture of 90% by weight of hydrogen and 10% by weight of carbon monoxide in the reduction step. At this pH, platinum now forms stable H.sub.2PtCl.sub.6 and can thus be transiently dissolved by oxidation of the platinum surface and subsequent reduction of the oxides. Here, the carbon monoxide added in the reduction step adsorbs on the platinum surface and thus prevents precipitation of platinum in the reduction step. The dissolution process of the platinum is also monitored by means of the measurement unit (not shown). As soon as all the platinum has been dissolved, the platinum solution is taken off from the collection vessel 50. The two metal solutions can now be worked up by precipitation of the respective metals by means of introduction of hydrogen.
[0032] A second working example of the apparatus is depicted in FIG. 2. In this working example, the oxidant feed conduit 33 and the reducing agent feed conduit 34 are not arranged between the stock vessel 20 and the first pump 35. Instead, a further subconduit branches off at the branching point of the first conduit 30 and both the oxidant feed conduit 33 and the reducing agent feed conduit 34 open into the end of this further subconduit. In this working example of the apparatus, these are not configured as Venturi nozzles but instead as valves. The subconduit of the first conduit 30 between the branching point and the oxidant feed conduit 33 or the reducing agent feed conduit 34 in this case does not serve to transport the electrolyte solution but instead exclusively to transport gas. Furthermore, the ozone decomposer 63 is not arranged downstream of the collection vessel 50 in this working example. Instead, the second conduit 40 branches a number of times before the second pump 43 and leads to the ozone decomposer 63 and an outlet conduit 64. When using this apparatus, the electrolyte solution is not already admixed with the gas required for the oxidation step, reduction step or flushing step before introduction into the fuel cell 10. Instead, ozone is firstly introduced into the fuel cell 10 in the oxidation step without introduction of the electrolyte solution, with unreacted ozone going into the ozone decomposer 63. Valves prevent gaseous ozone from getting to the outlet conduit 64 or into the pump 43. The aqueous electrolyte solution is then passed through the fuel cell 10 in order to take up metal ions. It is then conveyed by means of valves through the second pump 43 into the collection vessel 50. This is followed by a flushing step in which nitrogen is conveyed through the fuel cell 10 and leaves the apparatus through the outlet conduit 64. In the reduction step, hydrogen (for reducing ruthenium oxides) or the hydrogen/carbon monoxide mixture (for reducing platinum oxides) is conveyed through the fuel cell 10 and likewise leaves the apparatus through the outlet conduit 64, and further electrolyte solution is then introduced into the fuel cell 10 in order to complex metal ions and convey these into the collection vessel 50. The second flushing step is once again carried out without use of the electrolyte solution only by introduction of nitrogen, after which an oxidation step can be commenced again. The change between the different electrolyte solutions and the work-up of the metal solutions is carried out in the same way as when using the apparatus as per the first working example of the invention.
[0033] A third working example of the apparatus, which is depicted in FIG. 3, provides for ozone and hydrogen to be produced by means of an electrochemical ozonizer 70. This is supplied with distilled water from a water tank 71; this water is fed by means of a third pump 72 into the electrochemical ozonizer 70. In the oxidation step, ozone is conveyed from the ozone outlet of the electrochemical ozonizer 70, which functions as oxidant feed conduit 33, through the first conduit 30 into the fuel cell 10. Electrolyte solution is subsequently conveyed from the first stock vessel 20a and the associated first pump 35a through the fuel cell 10. The generation of ozone at the same time forms a mixture of hydrogen and water vapor. This is conveyed through the hydrogen outlet of the electrochemical ozonizer 70, which functions as reducing agent feed conduit 34a, into a tank 36 and collected there. In the reduction step, the hydrogen/water mixture is firstly conveyed from the tank 36 into the fuel cell 10 and electrolyte solution is subsequently conveyed from a second stock vessel 20b by means of the associated first pump 35b into the fuel cell 10. A further first pump 35c is arranged in the first conduit 30 in such a way that it can transport the water/hydrogen mixture. Downstream of this first pump 35c, there is also a further reducing agent inlet 34b which is configured as a Venturi nozzle. Carbon monoxide can be introduced by means of this reducing agent inlet 34b into the water/hydrogen mixture in the reduction step, or nitrogen can be introduced into the stream of the electrolyte solution from the second stock vessel 20b in the flushing step. When using this apparatus, the flushing step is carried out only after the reduction step and before the next oxidation step, but not after the oxidation step and before the following reduction step. As regards the use of different electrolyte solutions and the work-up of the metal solutions, the procedure as in the preceding working examples is employed.
[0034] FIG. 4 shows a fourth working example of the apparatus. This makes continuous operation of the electrochemical ozonizer 70 possible. The hydrogen/water mixture, which in the reduction of platinum oxides is additionally admixed with carbon monoxide, is here conveyed by suitable switching of valves in the first conduit 30 either through the anode inlet connection 31 or through the cathode inlet connection 32 into the fuel cell 10. At the same time, ozone is introduced into the fuel cell 10 through the other of the two connections 31, 32. Both the ozone and the reducing gases are mixed with electrolyte solution from two stock vessels 20a, 20b before they go into the fuel cell 10. Switching of the valves enables the oxidation step or the reduction step to be carried out alternately at the cathode and the anode. Here, the solutions from the oxidation at the one electrode and the reduction at the other electrode combine in the second conduit 40. The flushing steps are carried out simultaneously at the two electrodes, with the valves in the first conduit 30 being set so that an electrolyte solution from the second stock vessel 20b is admixed with nitrogen from the further reducing agent feed conduit 34b and is then conveyed to the anode inlet connection 31 and simultaneously to the cathode inlet connection 32. During the flushing steps, the electrochemical ozonizer 70 is switched off.
[0035] An apparatus as per the fifth working example of the invention is depicted in FIG. 5. This is designed to convey the electrolyte solution through the circuit a number of times. For this purpose, it is fed from a stock vessel 20 into the first conduit 30 and passed through the fuel cell 10. Through the second conduit 40, it is subsequently recirculated at a branching point of the first conduit 30 and the second conduit 40 into the first conduit 30. Downstream of this branching point, it can, depending on the process step, it can be admixed with ozone, nitrogen or hydrogen or a hydrogen/carbon monoxide mixture through the oxidant feed conduit 33 or the reducing agent feed conduit 34. When it has taken up all of a dissolved metal, the electrolyte solution can be pumped back into the stock vessel 20 and taken off from this by suitable switching of valves. A new electrolyte solution having a different pH is subsequently introduced.
[0036] In a sixth working example of the invention, a further apparatus as depicted in FIG. 6 is provided. This too allows the electrolyte solution to be conveyed continuously in a circuit. However, the stock vessel 20 is arranged so that its outlet opening 21 is connected to the first conduit and its inlet opening 22 is connected to the second conduit and it thus forms part of the circuit. The measuring unit 23 for determining the metal content of the electrolyte solution, which is not shown in the other working examples, is arranged in the stock vessel 20 in this working example. As soon as the recovery of a metal is concluded, a valve at the outlet opening 21 of the stock vessel 20 is closed and the entire electrolyte solution is pumped back into the stock vessel 20 and taken off from the latter via an offtake opening 24. The stock vessel 20 is then filled with a different electrolyte solution in the same way as in the fifth working example of the invention.
