KR20060067973A - An electrolytic cell for removal of material from a solution - Google Patents

Abstract

Disclosed is an electrolytic cell for removal of material from a solution. The cell comprises a cavity for receiving the solution, a rotatable electrode located within the cavity, a counter-electrode in spaced relation to the rotatable electrode, and an ultrasonic generator coupled to said cavity for directing ultrasonic energy toward the rotatable electrode to displace solid material extracted from the solution by an electrochemical reaction. The rotatable electrode may form a cathode, and the counter-electrode may form an anode, wherein metal in the solution is deposited on the cathode as a metal powder, such that the ultrasonic energy displaces the metal powder from the cathode. Alternatively, the rotatable electrode may form an anode, and the counter-electrode may form a cathode, wherein organic waste in the solution is deposited on the anode, such that the ultrasonic energy removes the deposited organic waste from the anode.

Description

ELECTROLYTIC CELL FOR REMOVAL OF MATERIAL FROM A SOLUTION

The present invention relates to an electrochemical method and apparatus for treating a solution by electrolytic extraction or electrooxidation.

The concept of recovering material from solution by electrolysis is not new. Many industries, such as plating processes, coal mine processes, and metal surface treatment processes, generate waste of solutions containing metal ions, and the recovery of the metals is environmentally and economically beneficial. Waste of solutions containing unrecovered metals increases the amount of sludge in the soil. Many metal recovery systems generally use mechanical devices such as blades to remove the deposited material from the electrodes. The use of mechanical devices has the disadvantage of increased wear, the risk of breakage and the tendency of the processing process to slow down.

U. S. Patent No. 4,028, 199 discloses a method of extracting powder from solution using a rotating electrode. The powder is removed from the electrode with a mechanical scraper. Since the scraper tends to leave a hard film that cannot be easily removed at the electrode after the primary removal, Applicants have found that such a system does not work sufficiently sufficiently.

Methods and apparatus for recovering metals from aqueous or non-aqueous solutions, and easy separation of electrochemically precipitated metals from basic cathodes are disclosed. Also disclosed are methods for removing organic dirt from aqueous or non-aqueous solutions. In order to remove the material precipitated in powder form at the rotating electrode, the material is efficiently removed from the electrode, using ultrasonic energy and using ultrasonic energy. It is important that the material must precipitate out in powder form. Applicants have found that the material is not suitable for removing material when it precipitates into a solid thin film.

Thus, according to one aspect of the invention, the invention provides an electrolytic cell for removing material from a solution. The cell converts ultrasonic energy into a rotating electrode to convert a solid material extracted from the solution into a powder by a cavity containing the solution, a rotating electrode located within the cavity, a counter electrode spaced apart from the rotating electrode, and an electrochemical reaction. And an ultrasonic generator connected to the cavity for supplying.

In one embodiment of the invention, the rotating electrode forms a cathode, the counter electrode forms an anode, the metal in the solution is deposited on the cathode in the form of a metal powder, the ultrasonic energy removes the metal powder from the cathode. In another embodiment of the present invention, the rotating electrode forms an anode, the counter electrode forms a cathode, and organic waste in solution precipitates on the anode, so that ultrasonic energy removes the deposited organic waste from the anode. The term "ultrasonic" should be understood to include acoustic vibrations that can generate sufficient cavitation to remove the powder from the electrode, whether or not it is clearly above the audible range. do. A suitable range is 16 to 40 KHz, with 25 KHz being preferred.

The ultrasonic generator includes an oscillator for generating alternating energy and a transducer connected to the cavity to convert the alternating energy into mechanical vibrations. There are two transducers connected to the cavity at an angle of 180 degrees opposite the cavity.

The rotating electrode may have a disk shape. The disk may consist of a flat sheet of flexible material consisting of an electrically conductive surface on one major surface. The relative electrode may be a coaxial rod in the cell. In addition, the battery may be a funnel shape.

The electrolytic cell further includes a collecting bin for collecting material removed from the rotating electrode, such as powdered metal from the negative electrode or organic waste from the positive electrode.

The electrolytic cell may have a device having a feature of stopping the liquid synergistic effect generated by the rotational movement of the rotating electrode. Such a device called a "meniscus-breaker" is necessary if the tangential velocity U of the electrode is higher than 1 m / sec. The magnitude (R) of the liquid level rising above the nominal value (the liquid level when the tangential velocity is zero) is represented by the following relation:

R = U ² / 4g

Where g is gravity acceleration.

The structure and size of the meniscus-breaker is determined by considering: a) the release of hydrogen, oxygen and other gases that can be produced at the electrode during the electrolysis process, b) through the central hole of the device to be treated. Liquid phase on top of the meniscus-breaker which must go, c) the presence of solid particles in the liquid phase (such as metallic powder). In view of these, the bottom of the meniscus-breaker must be conical or pyramid-shaped, whereas the top must be similar in shape to the inverted top of the bottom, thus having an overall hourglass shape. The top allows the liquid charged with solid particles (mostly metal) to return to the cell by gravity, whereas the bottom must allow gas to be discharged upwards with respect to the central hole of the meniscus-breaker. There is an angle in the part.

The meniscus-breaker must be placed below the nominal value of the liquid in the cell to be efficient. The edge of the meniscus-breaker must fit snugly against the inner wall of the cell so that no liquid flows between the wall and the meniscus-breaker.

The electrolytic cell includes a collecting portion for collecting the material removed from the rotating electrode, such as metal powder powdered from the negative electrode or organic waste formed from the positive electrode.

In still another aspect, the present invention provides a method for producing a metal comprising: passing a solution containing a metal into an electrolytic cell having a positive electrode and a negative electrode, and at the same time supplying a direct current to the solution between the positive electrode and the negative electrode so that the metal can be deposited as a powder on the negative electrode. It provides a method for electrolytic collection of metal comprising the steps of rotating the cathode during precipitation and supplying ultrasonic energy to the cathode to remove the powdered metal. Ultrasonic energy may be periodically supplied to the cathode.

The electrolytic cell may have a coolable hollow rotating electrode; Thus, it has a low melting point found in the aluminum extraction industry (the bauxite process) and can be used for the electrolytic extraction of metals such as gallium present in hot electrolytes. In this use, the gallium powder produced when the rotary electrode is negatively polarized does not use ultrasonic energy, but removes the cathode from the hot electrolyte, so that another liquid, preferably gallium, is at a temperature higher than the melting temperature. Recovered by immersion Therefore, the powder melts from the cathode and can be easily recovered as a precipitate of solid metal when the liquid is cooled below the melting point of gallium. There are a myriad of methods, devices and chemicals used to cool cavity rotating electrodes. That is, any combination of methods, devices, and chemicals for cooling the electrode surface can be used.

In yet another aspect, the present invention provides a method for producing an organic compound comprising: passing a solution comprising an organic compound through an electrolytic cell having a positive electrode and a negative electrode, and at the same time supplying a direct current to the solution between the positive electrode and the negative electrode so that the organic compound can be oxidized at the positive electrode Rotating the anode during oxidation, and supplying ultrasonic energy to the anode for cleaning the surface of the anode. Ultrasonic energy may be periodically supplied to the cathode.

There are many advantages to using the present invention. First, the present invention recovers metals from diluted electrolytes, more specifically from solutions with a total metal concentration ranging from 0 ppm to 3000 ppm, preferably from 20 ppm to 500 ppm. In addition, the present invention obtains the metal in powder form that can be removed from the rotating electrode without using a mechanical device such as a blade to remove the metal, thereby providing economical recovery of the metal from the solution. The powdery metal precipitate is easily removed from the rotating electrode using ultrasonic energy. Thereafter, the removed powder metal can be recovered using a suitable filtration system. The separation is simpler when the rotating electrode is the cathode.

Third, using ultrasonic energy to remove precipitates from the rotating electrode, at the same time, does not require the use of inorganic acids or other toxic chemicals for later use of the surface of the electrode. Fourth, the ultrasonic device of the present invention can be used to clean the surface of the rotating electrode from the organic deposit when the rotating electrode is positively polarized for electrooxidation, thereby avoiding a complicated method for cleaning the conductive surface. However, the device is configured such that the rotating electrode is erected. Thus, the device can be inspected, cleaned or repaired as desired.

The present invention also selectively purifies the strong electrolyte from the undesirable low concentrations of metallic dirt present in the strong electrolyte. In addition, the present invention is used to remove organic impurities present in low concentrations in inorganic or organic conductive electrolytes by electro oxidation. Preferred electrochemical reactions are achieved according to the induction electrode of the rotating electrode.

The present invention is more used to recover metals during plating and coal mining processes, but can also be used for other kinds of industries such as metal smelting. The recovery of metal reduces the amount of waste produced when the apparatus is installed upstream of the wastewater treatment system, thus reducing the amount of sludge in the soil.

Other aspects and advantages of embodiments of the invention will be readily apparent to those skilled in the art in light of the following description.

Embodiments of the present invention will be described with reference to the accompanying drawings.

1 is a high illustration of an electrolytic cell in accordance with the teachings of the present invention.

FIG. 2 is a schematic cross-sectional view of a battery cavity of the electrolytic cell in FIG. 1.

3 shows the electrolytic cell in FIG. 1 used industrially.

Certain representative embodiments of the materials, devices, and manufacturing processes of the present invention will be described in detail for purposes of illustration only. In particular, it is intended that the present invention not be limited to the methods, materials, conditions, limitations of the process, apparatuses, and the like recited herein.

The device provided in the present invention can be used for electrolytic extraction of metals or for oxidizing organic compounds. The operation of the device is selectively charged by changing the polarization of the rotating electrode, as follows.

Referring to FIG. 1, the electrolytic cell 10 includes a battery housing 12. The battery housing defines a battery cavity 14. The shape of the housing 12 in the electrolytic cell 10 is not limited, and may be made of any suitable material as long as the housing is electrically insulated from the electrodes. In general, the housing is cylindrical although other forms are possible. In this embodiment, it appears in the form of a funnel.

Rectifier 16 provides the necessary current and voltage between the anode and cathode to produce powder precipitates when the rotating electrode is negatively polarized or to oxidize organic dirt when the rotating electrode is positively polarized. The current is provided to the electrodes by electrical busbars 26 and 28. At least two electrodes, the cathode and the anode, are connected to the cathode and anode busbars 26 and 28, respectively. The rotating electrode can be polarized negatively or positively. The rotating electrode refers to the working electrode and the stop electrode refers to the counter electrode.

The housing 12 includes an inlet 18, a flow passage 20 for supplying a solution to be treated into a cell 10 in a storage tank (not shown) and an outlet 22 for removing the solution. This is accomplished by the pump 24. As a result of the electrochemical reaction, when the powder precipitates, the metal or organic dirt in the solution will be depleted. The depleted solution is transferred to a wastewater purification apparatus through a tank 32 including a wastewater filter 52. In the case of a solution containing copper, it is found that even in the precipitation step, some powder is removed and conveyed to the filter 52 together with the depleted solution.

The current is periodically interrupted and ultrasonic energy is used at the electrode to remove the powder. Typically the current can be stopped for 1 to 4 minutes every 24 to 36 hours. Typically, the rotational speed of the rotating electrode is reduced by 25% during the removal step.

When the powder is removed from the electrode using ultrasonic energy, the removed powder is passed along with the liquid flowing through the outlet and then passes through the filter 52 for removal. Since the liquid flowing in the cell at this stage is not completely removed, the liquid remaining after the tank 32 is transferred to a buffer tank (not shown) in addition to the wastewater purification apparatus. The liquid in the buffer tank can continue to return to the cell for further processing during the next precipitation step.

In accordance with the principles of the present invention, the cell 10 may include an oscillator 30 and an ultrasonic generator 31 which sends ultrasonic energy from the rotating electrode during the powder removal step.

2, the rotary electrode 40 is a separate component separate from the housing mounted on the drive shaft 60. In FIG. 2, the rotating electrode 40 is shown in a drum shape with a cylindrical counter electrode 42 having a fixed center. The exact shape of the rotary electrode 40 depends on the metal or organic dirt to be recovered. For example, the rotating electrode 40 may be a frustoconical having a larger diameter at the shortest end toward the circular upper layer opening of the electrolytic cell. Otherwise, the rotating electrode may be V-shaped with an opening at the bottom and a wide opening at the top. The rotating electrode includes a plate on two sides and a spacer member therebetween. Other shapes are also possible, such as cylinders, disks or grooved cylinders, multi-disc, hollow ellipse shapes. In any shape, the rotating electrode is an integral structure comprising a carrier with a conductive element on at least one side, of which metal is suitable.

The rotating electrode 40 may be a cavity disk. This shape is a simple mechanical structure. The rotating electrode generally consists of a flat sheet of flexible material having one electrically conductive surface on one major surface and an electrically non-conductive surface on the other, and protective means for folding the sheet and holding it in place. Suitable conductive materials include stainless steel, titanium and aluminum alloys thereof, or other conductive materials. There is no limitation on the tangential speed of the rotating electrode as long as the device is quickly installed and deemed necessary for the process.

The counter electrode 42 is also located within the battery cavity 14. The material of the counter electrode 42 is not limited to a specific method, and may be selected from materials conventionally used in the art. Materials available may include stainless steel, platinum titanium, lead or graphite, among other materials.

Regardless of the purpose of using or operating the device, the working electrode is to rotate. The rotating electrode is the electrode where the desired reaction takes place. Thus, the rotating electrode can be polarized negatively or positively.

The shapes of each of the electrodes 40 and 42 and the electrolytic cell 10 should all correspond to each other. For example, when the anode is rod-shaped, the axis of the anode coincides with the axis of the electrolytic cell and is cylindrical. The negative electrode is cylindrical, and in the case of surrounding the cylindrical positive electrode, the cell may be tubular. Alternatively, the battery is in the form of a box and can be divided into a negative electrode portion and a positive electrode portion by partitions. In the illustrated embodiment, the cell is cylindrical, both the positive and negative electrodes are cylindrical and spaced from each other.

The supply portion 16 of direct current is connected between the positive electrode and the negative electrode by leads 26 and 28 so that a current flows. When the rotating electrode is negatively polarized, the metal ions of the solution in the cavity move to the cathode where the metal is deposited. The cathode therefore rotates to promote mass transfer and reduce the thickness of the diffusion layer. The cathode is rotated by means such as a rotating drive shaft made of the same material as the cathode. The rotation of the negative electrode is made using a battery motor (not shown) via a speed controller (not shown). The rotary electrode 40 is shown to rotate clockwise, but the rotation direction may be counterclockwise.

When one or more rotating electrodes 40 are used to treat a particular volume of solution, they may be connected in parallel or in series to obtain the desired degree of contamination of the solution to be treated. Each rotating electrode 40 can be operated under similar or different modes of operation.

3 illustrates the electrolytic cell of FIG. 1 used industrially. The solution from the storage tank 50 is processed by the pump 54 and pumped into the cell 10. The cell is equipped with an ultrasonic numerical detector that regulates the operation of the pumps 24 and 54 to maintain the liquid in the cell at a desired value.

The solution flowing out of the bottom of the cell 10 flows into the tank 32 including the filter 52 to remove powder associated with the liquid discharged out of the cell 10.

The filter 52 may include a filter bag arranged for flowing liquid through the wall for later removal and for precipitating powder into bags. Any suitable filter technique is available for this purpose.

The bus bar 26 is electrically connected to the rotating electrode 40 by a brush connector 62 in contact with the drive shaft 60.

The drive shaft 60 is driven by rotation by the motor 64 and the pulley system 66. The drive shaft rotates in the bearing 68.

Preferably, the electrolytic cell may be provided with an apparatus 27 called "meniscus-breaker" which eliminates the meniscus synergistic effect which occurs when the tangential velocity is higher than 1 m / sec. The device 27 has a Chinese hat shape, which is in the form of a disk with a central cavity 27a, which disk has a top and bottom 27b that are narrower inwardly of the central cavity 27a. do. The device prevents the meniscus from escalating to the cell while the gas formed in the cell is discharged.

In operation, the negative electrode and the positive electrode are placed in the cell 10. The inlet is connected to a storage tank that stores the solution to be treated, and the solution is pumped from the tank to the cell by a pump to fill the cavity and close the circuit between the cathode and the anode. While it is expected to be used mostly in aqueous media, in certain cases it may be used in non-aqueous solutions or electrolytes (such as ethanol, benzoic acid, etc.). Preferably, a solution sufficient to submerge the cathode and anode is pumped into the cavity. The solution is pumped to fit the cell cavity. The total metal concentration of the solution for electrolysis is 0 ppm to 3000 ppm (mg / L), preferably 20 ppm to 500 ppm (mg / L).

The cell may be supplied in the form of a current such as direct current, alternating current, pulse, periodic reverse pulse, or the like. The positive and negative electrodes of the electrolytic cell are connected to rectifiers that control the application of power to the positive and negative electrodes.

 The apparatus of the present invention can be used to produce metal powder when the rotating electrode is negatively polarized. The powder may comprise metals or alloys in pure form or in metallic hydroxides or oxides. The definition of powder is broad (grain size, shape, metal ceramics, metals, alloys, etc.). Since the powder is formed instead of the compressed film of the metal or alloy, it is possible to remove the metal from the cathode using ultrasonic waves (described below).

Precipitation of the metal powder is achieved under strict control of the process limiting elements. The limiting factor to be controlled is through proper adjustment of the voltage, current density at the cathode (which pushes towards the limiting current), cathode rotation speed, plating time, and pH to ensure that the metal precipitates (reduces) as a powder at the cathode. Electrolytic conditions, composition, temperature, conductivity, viscosity, concentration and other limiting factors. Voltage and current are selected by fixing the value of the current flowing through the electrode to an optimal value for the range of concentrations found in a particular application. The current value is determined experimentally and is present depending on the particular application when the device is installed. For example, to produce zinc powder from an electrolyte containing only 100 ppm of zinc, a 0.5 meter diameter (double the width) disc rotates at 175 rpm with a current density of 60 mA / cm 2. If the metal concentration is different, the electroextraction conditions will also be different. If the metal is copper present at the same concentration instead of zinc, the rotational speed and current will also be different. The extraction conditions are determined separately for each case.

The metal powder generated at the cathode may be periodically removed by breaking current and using ultrasonic energy. Metal precipitation removal cycles can vary from one electrolyte to another. The amount of precipitation preferably does not exceed 10% of the distance between the anode and the cathode. For example, since the spacing between the preferred electrodes is 2 cm, 0.2 cm thick precipitates can be removed using an ultrasonic device. Powder removal conditions may vary from case to case. For example, the powder may be removed according to the coulomb or thickness determined according to the characteristics of the powder and the composition of the electrolyte.

The ultrasonic generator 30 supplies alternating energy at an excitation frequency within the ultrasonic range, such as 16 kHz to 40 kHz, preferably 25 kHz. Ultrasonic electrical energy is converted into mechanical vibrations of ultrasonic waves at frequencies corresponding to excitation frequencies. The vibration generated by the transducer 31 flows directly to the cathode such that cavitation can occur at the cathode surface. The effect removes metal powder from the electrode surface. For example, to remove zinc powder precipitates from the rotating electrode, two to four minutes of 20% high intensity ultrasound at 25 kHz every 24 hours of precipitation is sufficient to drop the powder from the rotating electrode. The dropped powder precipitates are continuously collected by the filter 52.

In one embodiment, two ultrasonic transducers 31, which are positioned at an angle of 180 degrees to each other, are installed (illustrated in FIG. 1). The width of the plate facing the vibrator is half the plate height, which is equal to the height of the rotating electrode. There is no limitation on the volume, position and size of the ultrasonic oscillator in the device, as long as the ultrasonic transducer faces the working electrode (rotary electrode) and does not disturb the electric field of the counter electrode.

The metal is precipitated into particles separated at the negative electrode, collected at the bottom of the cell, preferably conical or having a funnel having a solid angle of 20 ° to 75 °, preferably 45 °, and the metal rises from the cell Precipitates as a weakly adsorbed precipitate that can be washed away from the membrane. Metal powder accumulated at the bottom of the cavity can be removed periodically or continuously through the bottom outlet or valve from which the plug is removed. The collector is located at the bottom of the cell and collects the powdered metal removed from the negative electrode. Powders can be collected by recovering metals from industrially treated water (plating mills, smelters, coal mines, etc.) or by producing specific powders from purified electrolytes. The electrolyte composition may be formed such that the metal powder consists of pure metal or alloy.

In addition, the device of the present invention can be used to oxidize organic compounds when the rotating electrode is positively polarized. The rotary electrode can remove organic dirt from the organic or inorganic electrolyte. If attachment of the rotating electrode occurs during such use, ultrasonic cleaning is performed using an ultrasonic generator. For example, phenol or cresol can be electrooxidized from 1500 ppb (μg / L) to 20 ppb (μg / L) using a rotating electrode and the cathode is made of stainless steel. The nature of the organic compound to be removed, its concentration, and the material used as the electrode such as the anode and the cathode are not limited. Rotary electrodes are most effective at removing organic compounds found in low concentrations in organic or aqueous solutions.

To recover the solution once treated by electroextraction or electrooxidation, the outlet is connected to the original tank in a closed-loop manner or to another tank for further use or treatment of the solution. When the rotating electrode is operated so that the treated solution conforms to treatment rules and regulations (or the specific process required for 3000 ppm to 1000 ppm zinc for chromate bath), the treated solution flows directly into the sewer. Can be. Otherwise, the treated solution can be connected (or recovered to the process) with a conventional wastewater treatment system. The flow rate of the liquid to be treated is the same as the volume of liquid entering the inlet and outlet out of the outlet.

It can be seen that the battery can be used repeatedly with the same positive electrode and negative electrode.

The method of the present invention can be illustrated in the following examples. These examples are provided to illustrate the present invention in more detail, but are not limited thereto.

Example 1

The solution containing 100 ppm zinc from the zinc chloride plating solution is reduced to 15 ppm by two steps: The first step is 80 mA / at a rotating electrode with a tangential velocity of 3.5 to 4.5 m / sec for a treatment time of 1.33 times the flow rate. A current density of 2 cm 2 is used, and the second step uses half the current density in the first step, but takes twice the processing time.

Example 2

The solution containing 200 ppm of copper from the copper acid plating solution was reduced to 15 ppm using a current density of 60 mA / cm 2 at a rotating electrode with a tangential velocity of 3.0 to 4.0 m / sec for a treatment time equal to 1.25 times the flow rate.

Example 3

A solution containing 200 ppm of copper from the nickel acid sulfamate plating solution is reduced to 30 ppm using a current density of 27 mA / cm 2 at a rotating electrode with a tangential velocity of 2.5 to 3.5 m / sec for a treatment time equal to 1.50 times the flow rate. .

Example 4

The solution containing 200 ppm tin from the tin chloride plating solution was reduced to 30 ppm using a current density of 40 mA / cm 2 at a rotating electrode with a tangential velocity of 3.0 to 3.5 m / sec for a treatment time equal to 1.15 times the flow rate.

Various modifications are possible without departing from the spirit and scope of the invention as defined in the appended claims.

The present invention obtains the metal in powder form that can be removed from the rotating electrode without using a mechanical device such as a blade to remove the metal, thereby providing economical recovery of the metal from the solution.

Using ultrasonic energy to remove precipitates from the rotating electrode, at the same time eliminates the need for inorganic acids or other toxic chemicals for later use of the surface of the electrode. The ultrasonic device of the present invention can be used to clean the surface of the rotating electrode from the organic deposit when the rotating electrode is positively polarized for electrooxidation, thereby avoiding a complicated method for cleaning the conductive surface.

The present invention also selectively purifies the strong electrolyte from the undesirable low concentrations of metallic dirt present in the strong electrolyte. In addition, the present invention is used to remove organic impurities present in low concentrations in inorganic or organic conductive electrolytes by electro oxidation.

Although the present invention is more used to recover metals during plating and coal mining processes, it can be used for other kinds of industries such as metal smelting. The recovery of metal reduces the amount of waste produced when the apparatus is installed upstream of the wastewater treatment system, thus reducing the amount of sludge in the soil.

Claims (30)

In an electrolytic cell for removing a substance as a powder from a solution, A cavity containing said solution; A rotating electrode located within the cavity; A counter electrode spaced apart from the rotating electrode; And And an ultrasonic generator connected to the cavity to supply ultrasonic energy to a rotating electrode to remove material extracted from the solution into powder by an electrochemical reaction. The method of claim 1, wherein the solution comprises a metal, the battery is arranged such that the rotating electrode to form a cathode, the counter electrode to form an anode, the metal in the solution is deposited on the cathode as a metal powder, The ultrasonic energy is configured to remove metal powder from a cathode. 3. An electrolytic cell according to claim 1 or 2, wherein the ultrasonic generator comprises an oscillator for generating alternating energy and a transducer connected to the cavity to convert the alternating energy into mechanical vibration. 4. The electrolytic cell of claim 3, comprising two transducers connected with the cavity at an angle of 180 degrees opposite the cavity. The electrolytic cell according to claim 1 or 2, wherein the negative electrode is a disk. 6. An electrolytic cell according to claim 5, wherein said disk consists mainly of a flat sheet of flexible material provided with an electrically conductive surface on one major surface. The electrolytic cell according to claim 1 or 2, wherein the battery has a funnel shape. 8. The electrolytic cell of claim 7, wherein said positive electrode is a coaxial rod in a housing. The electrolytic cell of claim 1 or 2, further comprising a capture filter for capturing the powder metal removed from the negative electrode. The method of claim 1, wherein the rotating electrode forms a positive electrode, the counter electrode forms a negative electrode, the organic waste in the solution is deposited on the positive electrode, the ultrasonic energy is removed to remove the organic waste precipitated from the positive electrode Electrolytic cell. The electrolytic cell of claim 10, wherein the ultrasonic generator includes an oscillator for generating alternating energy and a transducer connected to the cavity so as to convert the alternating energy into mechanical vibration. 12. An electrolytic cell according to claim 11 comprising two transducers connected with the cavity at an angle of 180 degrees opposite the cavity. 11. The electrolytic cell of claim 10, wherein said positive electrode is a disk. 14. An electrolytic cell according to claim 13, wherein said disk consists mainly of a flat sheet of flexible material having an electrically conductive surface on one major surface. 11. The electrolytic cell of claim 10, wherein said battery is in funnel shape. The electrolytic cell of claim 15 wherein said negative electrode is a coaxial rod in said housing. An electrolytic cell solution for removing substances from a solution, A cavity containing said solution; A rotating electrode located within the cavity; And And means for preventing a meniscus synergistic effect that occurs when the tangential velocity of the rotating electrode is higher than a predetermined value. 18. The electrolytic cell according to claim 17, wherein the means for preventing the meniscus increasing effect comprises a disk having an inclined surface that becomes narrower toward the inside of the central cavity at the outer periphery of the disk. 18. The electrolytic cell of claim 17, wherein said predetermined value is about 1 m / sec. 18. The electrolytic cell of claim 17, wherein the means is geometrically arranged to allow liquid and solid particles to flow downward and to allow gas discharged from the cell to be discharged upwards. In an electrolytic cell for removing a substance as a powder from a solution, A cavity containing said solution; And An electrolytic cell comprising a cavity cooling rotary electrode which electrolytically extracts metal from an electrolyte at a temperature above the melting point of the metal. 22. The electrolytic cell of claim 21, wherein said metal is gallium. Passing a solution comprising a metal through an electrolytic cell having a positive electrode and a negative electrode; Supplying a direct current to a solution between an anode and a cathode such that the metal can be deposited on the cathode as a metal powder; Rotating the cathode during precipitation; And And supplying ultrasonic energy to a cathode to remove the powdered metal. 24. The method of claim 23, further comprising periodically interrupting the direct current and supplying ultrasonic energy supplied to a cathode while the direct current is interrupted. Passing the solution containing the organic compound through an electrolytic cell having a positive electrode and a negative electrode; Supplying a direct current to a solution between the positive electrode and the negative electrode so that the organic mixture can be oxidized at the positive electrode; Rotating the anode during oxidation; And And supplying ultrasonic energy to the anode to clean the surface of the cathode. 27. The method of claim 25, further comprising periodically interrupting the direct current and supplying the ultrasonic energy to a cathode while the direct current is interrupted. 27. The method of claim 26, wherein the direct current is cut off every 1 to 4 minutes every 24 to 36 hours. An apparatus for extracting a substance from a solution, A cavity containing a solution; A rotating electrode located within the cavity; A counter electrode spaced apart from the rotating electrode; Ultrasonic energy supply unit for supplying the ultrasonic energy to the rotary electrode and the counter electrode under the condition that the material is precipitated to the rotating electrode by a powder by an electrochemical reaction; And And an ultrasonic generator coupled to the cavity to supply ultrasonic energy to the rotating electrode to remove powder extracted from the solution. 29. The apparatus of claim 28, further comprising a device for arresting the rise of the meniscus while the electrode rotates at high speeds. 30. The device of claim 29, wherein the device is a disk comprising an internal cavity having an inclined surface that narrows in the direction of the internal cavity.

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