EP1932951A1 - Electrode basket with pulsed current supply - Google Patents

Abstract

The device comprises a current supply, an electrode, preferably anode, a basket and a pro basket. A counter electrode, preferably cathode is provided outside the basket. The electrode basket comprises a bulk chamber for filling with bulk material. The current supply provides current with a periodic variable current strength and/or a periodically reversible current flow to one of the electrodes.

Description

The invention relates to a device for the electrolysis of at least one anodic or cathodic, preferably anodic, soluble and at least one insoluble component containing bulk material, comprising at least one power supply and at least one electrode, preferably anode, basket and per basket at least one provided outside of the basket Counter electrode, preferably cathode, wherein the electrode basket comprises: a bulk material space for filling with bulk material, an adjoining sludge space for receiving emerging electrode sludge, an electrode, preferably an anode, and arranged between these spaces, preferably via a drive mechanism movable separating element.

AT 407 996 B describes an apparatus for the electrolysis of bulk material with anodically soluble constituents, wherein each anode is accommodated in an anode housing. There is an upper bulk material space and a lower sludge space available, which are separated by a separating element, which also serves as the sole anode and as a friction element for crushing the bulk material. The current flow is continuous with an amplitude.

If devices according to the prior art are used for the electrolysis of larger quantities of bulk material, clumping of the bulk material occurs and deposits on the electrode. The flow of current from the anode through the bulk material is made more difficult. Also often not the entire bulk material is uniformly subjected to electrolysis.

The object of the invention is now to provide a device for the electrolysis of bulk material, which prevents clumping of the bulk material and the formation of deposits on the electrodes and allows a uniform electrolysis of larger amounts of bulk material.

According to the invention this is achieved in that the power supply a current with a periodically variable current intensity and / or a periodically reversible current flow direction at at least one of the electrodes.

The variable current intensity and / or the periodic reversal of the current flow direction on at least one of the electrodes causes bulk material clumped on or in the vicinity of the electrode to be dissipated and / or dissolved by varying the current intensity and / or by reversing the current. For example, when the separator is used as the anode, cathodically soluble residue is deposited on the anode, which can be easily detached and / or dissolved in this way. As a result, less residues are deposited on the electrode, and the electrolysis can proceed unhindered.

In one embodiment, the separating element simultaneously serves as an electrode, preferably an anode. This is advantageous because no electrode, so no additional component, must be provided in the electrode basket. The design effort is considerably reduced.

In one embodiment of the invention, the current flow direction is reversible after a period of about 1 μs to about 10,000 s for a period of about 0.01 μs to about 5 s. After an electrolysis period of about 1 .mu.s to about 10,000 s, a residue may have deposited on the electrode (s), which residue can be removed and / or dissolved by reversing the current flow direction. The duration of the reversal of the current flow direction from about 0.01 μs to about 5 s is sufficient to dissipate and / or dissolve the residue, but at the same time the reversal time is so short that the overall reaction is not seriously disturbed.

Preferably, the current flow direction is reversible after a period of about 10 μs to about 1,000 s for a period of about 0.1 μs to about 1 s. This duration of electrolysis or the duration of the reversal of the current flow direction is generally sufficient to dissolve and / or dissolve residues on the electrode (s) and to continue the electrolysis as originally planned.

In one embodiment of the invention, the current intensity can be switched between at least two values. Thereby, a pulsation can be carried out, which causes a dissolution of the soluble component (s) and / or of deposits. With a higher current, a larger amount of bulk material can be better electrolyzed, as well as, if the electrolysis is already more advanced, the remaining bulk material with a high proportion of insoluble components are better electrolyzed.

In one embodiment, the power supply to at least one of the electrodes is periodically interruptible. By interrupting the power supply, the continuous deposition of residues on the electrodes is prevented.

In another embodiment, the power supply is interruptible after a period of about 1 μs to about 10,000 s for a period of about 0.01 μs to about 5 s. This duration is generally sufficient to prevent deposition of residues.

Preferably, the power supply is interruptible after a period of about 10 μs to about 1,000 s for a period of about 0.1 μs to about 1 s. This duration of the interruption is sufficient to prevent deposits, at the same time the entire electrolysis is not disturbed by it.

In one embodiment of the invention, to support the electrolysis, at least one further electrode, preferably anode, with the same polarity as the electrode, preferably anode, is provided in the electrode basket. The current flowing to or from the electrode decreases with increasing distance from the electrode; It thus creates a current gradient. The current therefore does not reach the entire bulk material with the same current. The attachment of at least one further electrode has the advantage that at a further point, preferably at several other locations, the bulk material is supplied to electricity and the electrolysis there can take place at a higher current than that was possible with conventional electrolysis.

At least one of the further electrodes in the bulk material space normally bounded by a wall or a frame may be attached to this wall or to the frame of the bulk material space. Such an attachment ensures that the electrodes are present in the vicinity of the bulk material without great constructive effort and can contact this well.

Alternatively or additionally, at least one of the further electrodes may be attached to the drive mechanism of the movable separating element. As a result, the at least one further electrode is moved along with the movement of the separating element. The movement of the electrodes makes a better contact with the bulk material, furthermore, the bulk material is thereby also mixed and, if appropriate, comminuted and therefore subjected to a better electrolysis reaction.

Again alternatively or in addition to the above two embodiments, at least one of the further electrodes may be attached to the movable separator. By this design, it is very easy to move the additional electrode together with the separator, so as to contact a larger proportion of the bulk material with the electrode directly.

Embodiments in which a plurality of electrodes are attached to the frame as a function of the amount of the insoluble portion and the amount of the bulk material are preferred.

In one embodiment of the invention, the or each electrode basket is in two parts in the form of an inner and an outer basket, wherein the inner basket is accommodated in and removable from the outer basket and the two baskets are in fluid communication with each other through an electrolyte solution. This separate construction of inner and outer basket allows easy removal, cleaning, filling, etc., as well as multiple use of the baskets.

In a preferred embodiment of the invention, the inner basket is relative to outer basket movably arranged and movable during the electrolysis. This movable arrangement is used for movement, for example, for shaking or shaking, possibly also for pivoting, the inner basket containing the bulk material. As a result, a mixing of the bulk material is achieved, whereby the bulk material is brought into better contact with the electrodes. Furthermore, agglomeration of the bulk material can be prevented or dissolved again by moving the inner basket.

In particularly preferred embodiments of the invention, the movable separating element serves as a friction element for comminution and / or disintegration of agglomerations of the bulk material. By forming the separating element as a means for comminution and / or disintegration of agglomerations of the bulk material, an additional comminuting agent can be avoided, which simplifies the construction of the device. The mincing causes the release of soluble inclusions in, for example, insoluble material which otherwise would have been inaccessible to electrolysis. This increases the yield.

In another embodiment of the invention, the bulk material space, the movable separating element and the drive mechanism are housed in the inner basket. By attaching these elements in the inner basket, the inner basket can be easily removed for repair in case of any mechanical affliction.

In yet another embodiment of the invention, the drive mechanism of electrically conductive material, such as titanium, protrudes beyond the upper edge of the inner basket, is connected to an external power source and is used to supply power to the movable separating element and optionally to one or more of the additional electrodes. By this simple construction, an effective power supply to the separator serving as an electrode and any additional electrodes provided thereon or on the drive mechanism is possible. Separate power supply lines can be omitted, which simplifies the construction of the entire device. Preferably, the drive mechanism is used to supply power to the movable Separating element and at least one further, attached to the drive mechanism and / or on the separator electrode. As a result, a plurality of electrodes is supplied with current by a power supply line. This is a structurally simple solution that helps to avoid additional power lines in the electrolysis device.

In these embodiments, the mechanism is preferably substantially covered or coated towards the counter electrode, preferably cathode, by electrically non-conductive material. This directs the flow of current from the mechanics to the bulk material and prevents direct flow of current from the mechanics to the counter electrode. This ensures that the electricity flows through the bulk material and can perform its work in the bulk material.

In another embodiment of the invention, the wall or frame of the bulk material space is made of electrically conductive material, e.g. Titanium, and is used to supply power to at least one other electrode attached thereto. As a result, several electrodes are in turn supplied with power with only one power supply line. Again, in such embodiments, the wall or frame is substantially covered or coated toward the counter electrode, preferably cathode, by electrically non-conductive material. As a result, the power supply is enabled again only at the desired locations and efficiently prevents corrosion of the wall or the frame.

In one embodiment of the invention, the inner basket is open at the top for inserting the movable partition member and for filling the bulk material and downwardly for discharging the electrode slurry. Due to this open design bulk material can be easily refilled and the electrode sludge can be easily removed, without having to resort to a complicated mechanism, which is defective prone. By simply refilling the bulk material and removing the electrode slurry, the device can be operated continuously.

In yet another embodiment of the invention, the inner basket is surrounded by a filtering membrane permeable to cations and anions. As a result, coarse filtration is achieved.

In another embodiment of the invention, the mud room is housed in the outer basket. This separation of the sludge space from the inner basket allows a better separation of the electrode sludge from the bulk material.

In one embodiment of the invention, the outer basket is made of an electrically non-conductive material, e.g. Plastic or ceramic. The outer basket does not participate in the electrolysis and remains unaffected by electrochemical contamination. Furthermore, plastic and ceramic are chemically inert materials that do not react with the electrolyte. Likewise, unwanted reactions are withheld, for example, half-full basket.

In a further embodiment of the invention, the outer chamber harboring the mud chamber is conically tapered downwardly to collect the electrode mud in the lower region of the outer basket. The electrode slurry thus falls into this conical taper and is collected there. The removal of the sludge in the course of the electrolysis reaction is thereby very easily possible.

In yet another embodiment of the invention, a suction opening for connecting a suction tube is provided at the lower end of the outer basket. Through this suction tube, the resulting electrode sludge can be easily, quickly and inexpensively removed from the electrolysis reaction.

In one embodiment of the invention, a sedimentation and / or filtration device is connected to the suction tube, wherein a return line for clarified liquid is provided in the electrode basket at the end of the sedimentation and / or filtration device. The return can be done in the cathode compartment and / or in the anode compartment. By this arrangement, the sludge can be continuously removed from the sludge room, be separated from the electrolyte and the clarified Electrolyte be recycled. The continuous operation therefore requires no interruption of operation by replacing the outer basket to remove the electrode slurry, whereby of course the bulk material can also be supplied continuously.

In a further embodiment of the invention, the outer basket is surrounded by an electrolyte solution penetrable and solid particles non-penetrable membrane or diaphragm. This allows collection of all sludge in the sludge compartment. It is therefore ensured that no electrode slurry passes into the construction surrounding the outer basket and the entire sludge can be removed from the electrolysis basket in order to then possibly further treat it and to extract valuable substances contained therein.

In yet another embodiment of the invention, the outer basket is surrounded by a cation or anion permeable membrane. By this design measure either only cations or only anions can penetrate the membrane. This enables "re-salting", i. in the outer basket, a cation or anion prevails, while outside of the outer basket prevails another cation or anion. A salt soluble in the outer basket may therefore form an insoluble salt outside the outer basket. Thus, a separation of the electrolytically dissolved substances can be made.

In one embodiment of the invention, windows are provided in the outer basket at least on one of the counter-electrode, preferably cathode, facing side, which are about the same size as or larger than the bulk material space and completely lined with a membrane. Through this membrane, the electrolyte liquid can move freely from the outer basket to the counter electrode and thus produce a charge balance. Sludge leakage, however, is prevented by this window; he remains in the outer basket.

In another embodiment of the invention, the membrane is made of electrically conductive material. Here, an additional current can be applied to the electrolysis process to support.

In a further embodiment of the invention, counter electrodes, preferably cathodes, are provided on both sides of the outer basket, and the outer basket has a membrane-clad window on both sides. This arrangement of electrodes on both sides of the outer basket causes more effective electrolysis because the current is not concentrated on one side. As a result, a more uniform electrolysis is achieved.

In a further embodiment of the invention, collecting devices for collecting electrode sludge are provided on the counter electrodes, preferably cathodes. As a result, a sludge produced at the counter electrodes is collected directly and can be supplied from there to a further treatment.

In a further embodiment of the invention, a plurality of electrode baskets are connected in series. By a serial connection of electrode baskets, only one current source is needed to supply the electrode baskets with a constant voltage. Only one rectifier is needed for all electrode baskets.

In another embodiment of the invention, a plurality of electrode baskets are connected in parallel. By a parallel connection of electrode baskets, only one current source is needed to supply the electrode baskets with a constant voltage, but a rectifier must be provided for each electrode basket.

Brief description of the drawings

Figures 1a to 1i show various pulse patterns used in the present invention. Fig. 1a shows a pulse pattern in which the inversion takes place with the same amplitude. Fig. 1b shows a pulse pattern in which the inversion occurs with low amplitude. Fig. 1c shows a pulse pattern in which the reversal takes place with a higher amplitude. Fig. 1d shows a pulse pattern in which an interruption of the power supply takes place before the reversal. Fig. 1e shows a pulse pattern in which the Power supply is discontinuous. Fig. 1f shows a pulse pattern in which the power supply oscillates between two values. Fig. 1g shows a pulse pattern in which the power supply is discontinuous with two different amplitudes. Fig. 1h shows a pulse pattern in which the power is supplied with two different amplitudes, then interrupted and then takes place with a negative amplitude. Fig. 1i shows a pulse pattern in which the power supply oscillates between two values and is then interrupted.

Figures 2a and 2b show a side view and a top view, respectively, of one embodiment of an inner basket of the invention in which another electrode is attached to a wall or to the frame.

Figs. 3a and 3b show a side view and a plan view of an embodiment of an inner basket of the invention, in which a further electrode is attached to the drive mechanism of the movable separating element.

Figs. 4a and 4b show a side view and a plan view of an embodiment of an inner basket of the invention, in which a further electrode is attached to the movable partition.

example

In one example of the present invention, a bulk material containing an anodic or cathodic, preferably anodic, soluble and an insoluble component is introduced into a bulk material space. The bulk material space can be accommodated in two-part design of the electrode basket in the inner basket. Preferably, the inner basket is surrounded by a filtering membrane permeable to cations and anions. The membrane can form together with existing support ribs or the wall or the frame the receiving basket for the bulk material. The bulk material may for example consist of granules or a powder or Zementationsniederschlägen and has a particle size of about 5 microns to about 15 mm, preferably about 50 microns up to about 10 mm, on. For example, the bulk material consists of an Ag / Cu matrix with a ratio Ag: Cu of about 70:30, but it can also be a ratio Ag: Cu of about 60:40 to about 80:20 or in a ratio of about 50:50 to about 90:10. The remaining portion of the bulk material, in about 18%, preferably 10 to 30%, consists of insoluble metals such as Au or platinum group metals and optionally of insoluble metal oxides or metal oxides which form in the anodic reaction, such as PbO ₂ , however Other insoluble metal oxides or other insoluble or sparingly soluble substances, such as chlorides, and optionally also soluble compounds such as the metals Fe, Ni, etc. Amphoteric metals may also be present, which are first dissolved and subsequently form insoluble oxides ,

In the bulk material space, a separating element 3 is present, which simultaneously serves as an electrode and preferably extends over substantially the entire width of the basket. The bulk material migrates from above in the direction of gravity down, while the current flows from the separator 3 upwards, so opposite to the bulk material. In addition, at least one further electrode 4 is present in the bulk material space, wherein the arrangement and / or the length are not essential to the invention. It can be arranged parallel to the separating element 3 but also at any angle thereto. Preferably, the at least one further electrode 4 is formed parallel to the separating element 3. The length may be shorter or longer than the separating element 3. Preferably, it is approximately the same length as the separating element 3. In one embodiment, two electrodes 4, which protrude at the respective opposite points in the bulk material space, together approximately the length of Divider 3 result. For example, the at least one further electrode 4 may be attached to the frame of the inner basket 1, but also on the drive mechanism 2 for the movable separating element or even on the separating element 3 itself, as described above and shown in the figures. The number of additional electrodes varies and is adjusted to the amount of the insoluble portion or the amount of the bulk material. Also, in the lower region of the bulk material space, the distance between the electrodes may be smaller than in the upper region.

Optionally, an electrode is also arranged in the mud room.

The inner basket 1 is preferably arranged movably relative to the outer basket. The connection can be made for example via joints, hinges or flexible connections. The inner basket 1 can thus be moved during the electrolysis by means of an external drive, e.g. shaken or pivoted, which allows a thorough mixing of the bulk material and at the same time prevents clumping of both the bulk material and the resulting reaction products. Furthermore, so come the electrically conductive particles repeatedly in contact and allow a continuous power line through the entire bulk material, whereby the entire bulk material acts as an anode.

Via the separating element 3 and the at least one further electrode 4, the bulk material is supplied power. As an example of the applied voltage and the applied current, about 0.1 to about 30 V or> 1000 A can be specified, but other voltages and currents can be used, depending on the composition of the bulk material and the element to be separated. It is also possible to use potentiometric control of the electrolysis. Also, the current can be varied. When using a Cu / Ag matrix, the voltage can be adjusted so that Cu goes into solution, but Ag does not. There remains a framework of Ag over. The tension can then be changed so that Ag also goes into solution. In this so-called "skeletal electrolysis", the electrode diameter is up to 5 mm.

The electrolyte used in the example is a sulfuric acid solution with a content of H ₂ SO ₄ of <12 M in order to deliberately bring CuSO ₄ into solution. Cu is then cathodically deposited in a purity of> 99% Cu. The temperature may for example be -5 ° C, but other temperature ranges are applicable, for example -10 ° C, 0 ° C, 5 ° C, 10 ° C, room temperature but also temperatures up to about 50 ° C or even about 90 ° C. In another example, a nitric acid electrolyte may be used, or even a hydrochloric acid electrolyte. The concentration of acids is generally about 12 M, but may be less be. The bulk material can also consist of> 60% platinum group metals. However, it is also possible to use another current-conducting or non-conducting electrolyte.

During the electrolysis, the applied current is preferably reversed for a short time, ie, the cathode becomes a cathode for a short time and an anode for a short time. This can be provided, for example, after an electrolysis period of about 1 μs to about 10,000 s for a period of about 0.01 μs to about 5 s. A preferred range is the reversal after a period of about 10 μs to about 1,000 s for a duration of about 0.1 μs to about 1 s. The turnaround time may be, for example, 100 μs, 200 μs, 500 μs, 700 μs, 1 s, 2 s, 3 s, 4 s, or 5 s, but is not limited thereto and may take any other value. This allows the dissolution and / or dissolution of originally deposited at the anode cathodic soluble deposits and vice versa. The electrode is thus freed from deposits. A formation of larger impurities at the respective electrodes can thus be avoided. Likewise, the current flow can be interrupted after an electrolysis period of about 1 μs to about 10,000 s for a period of about 0.01 μs to about 5 s. A preferred range is the interruption after a period of about 10 μs to about 1,000 s for a duration of about 0.1 μs to about 1 s. The interruption duration may be, for example, 100 μs, 200 μs, 500 μs, 700 μs, 1 s, 2 s, 3 s, 4 s or 5, but is not limited thereto and may also assume any other value. This also allows the dissolution and / or dissolution of originally deposited at the anode cathodic soluble deposits and vice versa. In Fig. 1 exemplary pulse patterns are shown schematically. 1a shows a pulse pattern in which the reversal of the current flow direction is carried out with the same amplitude as before the electrolysis. FIG. 1b shows a pulse pattern in which the reversal of the direction of current flow is carried out with a lower amplitude than the electrolysis. In Fig. 1c, a pulse pattern is shown in which the reversal of the direction of current flow is made with a higher amplitude than the electrolysis. Fig. 1d again shows a pulse pattern in which there is a power supply break between the polarity reversal. This break can be like be stated above. In Fig. 1e, a pulse pattern is shown in which the power supply is interrupted. Fig. 1f shows a pulse pattern in which the power supply oscillates between two values. Fig. 1g shows a pulse pattern in which the power supply is discontinuous with two different amplitudes. Fig. 1h shows a pulse pattern in which the power is supplied with two different amplitudes, then interrupted and then takes place with a negative amplitude. Finally, Fig. 1i shows a pulse pattern in which the power supply oscillates between two values and is then interrupted. However, other pulse patterns known to those skilled in the art may be used. The invention is not limited to those enumerated. The times for a pulse train can be chosen arbitrarily, but are preferably as stated above. With a higher current, a larger amount of bulk material can be better electrolyzed, as well as, if the electrolysis is already more advanced, the remaining bulk material with a high proportion of insoluble components are better electrolyzed.

During the electrolysis, the separating element 3 is also preferably moved, which in such cases is movably arranged via a drive mechanism 2. Moving the separating element 3, which simultaneously serves as a friction element here, causes comminution and / or disintegration of the bulk material and thus contributes significantly to improved electrolysis. Any additional electrodes 4 of the present invention attached to the drive mechanism 2 (FIGS. 3 a, 3 b) or to the separation element 3 itself (FIGS. 4 a, 4 b) are simultaneously moved along and can thus contribute to mixing and comminution.

The power supply may in this case preferably take place via the drive mechanism 2, the drive mechanism 2 being particularly preferably substantially covered or coated towards the counterelectrode by electrically non-conductive material. This keeps unwanted reactions behind. However, the power supply can, especially in cases where at least one additional electrode 4 is attached to the frame, also on this take place, which for this purpose consists of electrically conductive material and also preferably to the counter electrode out with electrically non-conductive Material is covered or coated. This also prevents unwanted electrolysis elsewhere.

During the electrolysis, the electrolytically soluble portion of the bulk material dissolves, while the electrolytically insoluble portion of the separating element 3 falls over into the sludge space. The separating element 3 may, for example, have openings with a size of about 20 μm to about 2 mm, preferably about 50 μm to about 1 mm, through which the insoluble particles may fall into the mud space underneath. The mud room is preferably mounted in an outer basket and tapers conically at the bottom. The outer basket is usually made of electrically non-conductive material, such as plastic. As a result, an undesirable reaction is avoided with a half-full basket. The conical taper at the bottom allows a simplified removal of the mud. This is all the more facilitated if a suction opening is present at the lower end, to which a suction tube can be connected. The suction tube may be connected to a sedimentation and / or filtration device as mentioned above, it being possible for a return line for clarified liquid to be provided in the electrode basket at the end of the sedimentation and / or filtration device. This arrangement is preferred when the electrolyte is to be circulated. The separation of the sludge takes place outside the electrode basket. It can be done for example by a filter, a centrifuge or other suitable means.

In one example, the outer basket is surrounded by a membrane permeable only to the electrolyte solution. This avoids sludge leakage. If, in preferred embodiments, the membrane is designed to be penetrated either by cations or by anions only, salification may also take place. A soluble component, for example a cation, can then go into solution, for example as sulfate, and be precipitated in the space separated by the membrane with another anion, for example nitrate. Conversely, an anion can also be dissolved, penetrate the membrane and then precipitate with another cation or otherwise undergo a reaction. Instead of this or any other membrane mentioned herein may also be Diaphragm or ionic conductor such as a solid membrane or a gel or any other material can be used, which has the same effect as the membrane.

In another example of the invention, the outer basket has windows through which electrolyte solution can pass. At the counter electrodes, for example, collecting devices for collecting reaction products that arise at this electrode are provided. Thus, reaction products can be easily recovered. Optionally, gaseous reactants, such as hydrogen, are formed at the counter electrode. This is advantageous because a costly further treatment or disposal of solid and / or liquid and / or dissolved reaction products is eliminated since gaseous products escape from the device. Gaseous reaction products can also be utilized energetically.

In one example of this invention, the electrode baskets are preferably connected in series. Thus, a constant voltage can be applied to a power supply line and only one rectifier is required for the entire electrode basket arrangement. Thus, with the anodic dissolution of Pt (Pt → Pt ⁴⁺ + 4 e ^- ) with a serial circuit with the same current, a higher yield can be achieved. But a parallel circuit of the electrode baskets is also possible.

Claims (36)

Device for the electrolysis of at least one anodic or cathodic, preferably anodic, soluble and at least one insoluble component containing bulk material comprising at least one power supply and at least one electrode, preferably anode, basket and per basket at least one provided outside the basket counter electrode, preferably cathode wherein the electrode basket comprises: a bulk material space for filling with bulk material, an adjoining sludge space for receiving resulting electrode sludge, an electrode, preferably an anode, and a separating element (3) arranged between these spaces, preferably via a drive mechanism (2),
characterized in that
the power supply provides a current having a periodically variable current intensity and / or a periodically reversible current flow direction at at least one of the electrodes. Apparatus according to claim 1, characterized in that the separating element (3) at the same time as an electrode, preferably anode, is used. Apparatus according to claim 1 or 2, characterized in that the current flow direction after a period of about 1 microseconds to about 10,000 s for a period of about 0.01 microseconds to about 5 s is reversible. Apparatus according to claim 3, characterized in that the current flow direction after a period of about 10 μs to about 1,000 s for a period of about 0.1 μs to about 1 s is reversible. Device according to one of the preceding claims, characterized in that the current intensity can be switched between at least two values. Apparatus according to claim 5, characterized in that the power supply to at least one of the electrodes is periodically interruptible. Apparatus according to claim 6, characterized in that the power supply to a duration of about 1 microseconds to about 10,000 s for a period of about 0.01 microseconds to about 5 s is interruptible. Apparatus according to claim 7, characterized in that the power supply after a period of about 10 microseconds to about 1,000 s for a period of about 0.1 microseconds to about 1 s is interruptible. Device according to one of the preceding claims, characterized in that to support the electrolysis at least one further electrode (4), preferably anode, with the same polarity as the electrode, preferably anode, is provided in the electrode basket. Device according to one of the preceding claims, characterized in that the bulk material space is bounded by a wall or a frame and at least one of the further electrodes (4) is mounted on the wall or on the frame of the bulk material space. Device according to one of the preceding claims, characterized in that at least one of the further electrodes (4) on the drive mechanism (2) of the movable separating element (3) is mounted. Device according to one of the preceding claims, characterized in that at least one of the further electrodes (4) is mounted on the movable separating element (3). Device according to one of the preceding claims, characterized in that the or each electrode basket is made in two parts in the form of an inner (1) and an outer basket, wherein the inner basket (1) in the outer basket is housed and removable from this and the two baskets communicate with each other through an electrolyte solution in fluid communication. Device according to one of the preceding claims, characterized in that the inner basket (1) is arranged movable relative to the outer basket and movable during the electrolysis. Device according to one of the preceding claims, characterized in that the movable separating element (3) serves as a friction element for comminution and / or disintegration of agglomerations of the bulk material. Device according to one of the preceding claims, characterized in that in the inner basket (1) of the bulk material space, the movable separating element (3) and the drive mechanism (2) are housed for it. Device according to one of the preceding claims, characterized in that the drive mechanism (2) made of electrically conductive material, such as titanium, projects beyond the upper edge of the inner basket (1), is connected to an external power source and for supplying power to the movable separating element (3) is used. Apparatus according to claim 17, characterized in that the mechanism (2) to the counter electrode, preferably cathode, is substantially covered or coated by electrically non-conductive material. Device according to one of the preceding claims, characterized in that the drive mechanism (2) for supplying power to the movable separating element (3) and / or the at least one further, on the drive mechanism (2) mounted electrode (4). Device according to one of the preceding claims, characterized in that the inner basket (1) upwards for insertion of the movable Separator (3) and for filling the bulk material and down to discharge the electrode slurry is open. Device according to one of claims 10 to 20, characterized in that the wall or the frame of the bulk material space consists of electrically conductive material, for example titanium, and serves to supply power to the at least one further, attached thereto electrode (4). Apparatus according to claim 21, characterized in that the wall or the frame to the counter electrode, preferably cathode, is substantially covered or coated by electrically non-conductive material. Device according to one of the preceding claims, characterized in that the inner basket (1) is surrounded by a filtering membrane which is penetrable for cations and anions. Device according to one of the preceding claims, characterized in that the mud chamber is accommodated in the outer basket. Device according to one of the preceding claims, characterized in that the outer basket made of an electrically non-conductive material, such as plastic or ceramic. Device according to one of the preceding claims, characterized in that the outer space containing the sludge space is tapered conically downwards to collect the electrode sludge in the lower region of the outer basket. Apparatus according to claim 26, characterized in that a suction opening for connecting a suction tube is provided at the lower end of the outer basket. Apparatus according to claim 27, characterized in that a sedimentation and / or filtration device is connected to the suction tube, wherein at the end of the sedimentation and / or filtration device a return line for clarified liquid is provided in the electrode basket. Device according to one of the preceding claims, characterized in that the outer basket is surrounded by an electrolyte solution penetrable membrane permeable to solid particles and / or diaphragm. Device according to one of the preceding claims, characterized in that the outer basket is surrounded by a penetrable by cations or anions membrane. Device according to one of the preceding claims, characterized in that in the outer basket at least on one of the counter electrode, preferably cathode, side facing windows are provided which are about the same size or larger than the bulk material space formed and completely lined with a membrane. Apparatus according to claim 31, characterized in that the membrane consists of electrically conductive material. Device according to one of claims 31 or 32, characterized in that on both sides of the outer basket counter-electrodes, preferably cathodes, are provided and the outer basket has on both sides in each case a membrane-clad window. Device according to one of the preceding claims, characterized in that there are provided on the counter electrodes, preferably cathodes, collecting devices for collecting electrode sludge. Device according to one of the preceding claims, characterized in that a plurality of electrode baskets are connected in series. Device according to one of the preceding claims, characterized in that a plurality of electrode baskets are connected in parallel.

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