EP1680530A4 - ELECTROLYTIC CELL INTENDED TO REMOVE A MATERIAL FROM A SOLUTION - Google Patents
ELECTROLYTIC CELL INTENDED TO REMOVE A MATERIAL FROM A SOLUTIONInfo
- Publication number
- EP1680530A4 EP1680530A4 EP04761844A EP04761844A EP1680530A4 EP 1680530 A4 EP1680530 A4 EP 1680530A4 EP 04761844 A EP04761844 A EP 04761844A EP 04761844 A EP04761844 A EP 04761844A EP 1680530 A4 EP1680530 A4 EP 1680530A4
- Authority
- EP
- European Patent Office
- Prior art keywords
- cathode
- electrolytic cell
- solution
- anode
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/007—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells of cells comprising at least a movable electrode
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/06—Operating or servicing
- C25C7/08—Separating of deposited metals from the cathode
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/34—Treatment of water, waste water, or sewage with mechanical oscillations
- C02F1/36—Treatment of water, waste water, or sewage with mechanical oscillations ultrasonic vibrations
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4676—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction
- C02F1/4678—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electroreduction of metals
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46119—Cleaning the electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46123—Movable electrodes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/16—Nature of the water, waste water, sewage or sludge to be treated from metallurgical processes, i.e. from the production, refining or treatment of metals, e.g. galvanic wastes
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4612—Controlling or monitoring
- C02F2201/46125—Electrical variables
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4616—Power supply
- C02F2201/4617—DC only
Definitions
- the present invention relates to an electrochemical method and apparatus for treating solutions either by electrowinning or electrooxidization.
- a method and apparatus for the recovery of metal from either an aqueous or non-aqueous solution, and facile separation of electrochemically deposited metal from an underlying cathode is disclosed. Also disclosed is a method for the destruction of organic contaminants from either an aqueous or non-aqueous solution. Both rely on the formation of a powder and utilize ultrasonic energy to remove the material deposited in powder form on a rotatable electrode from the electrode, which permits efficient removal of the material. It is important that the conditions be such that the material be deposited in powder form. The applicants have found that it is not feasible to dislodge the material if it becomes deposited as a solid film.
- the invention provides 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 as a powder by an electrochemical reaction.
- the rotatable electrode forms a cathode
- the counter-electrode forms an anode
- 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.
- the rotatable electrode forms an anode
- the counter-electrode forms 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.
- ultrasonic embraces sound vibrations capable of causing a cavitation effect sufficient to dislodge the power from the electrode whether strictly beyond the audible range or not.
- a suitable range is 16 to 40 KHz, with 25 KHz being preferred.
- the ultrasonic generator may comprise an oscillator for producing alternating-current energy, and a transducer coupled to the cavity for converting the alternating-current energy to mechanical vibrations. There may be two transducers coupled to the cavity at 180 degrees across the cavity.
- the rotatable electrode may be in the shape of a disk.
- the disk may be formed of a generally flat sheet of flexible material with an electrically-conductive surface provided on one major surface thereof.
- the counter-electrode may be a rod coaxial within the cell. Further, the cell may be funnel-shaped.
- the electrolytic cell may further comprise a collecting bin for collecting the material removed from the rotatable electrode, such as powdered metal from the cathode, or organic waste from the anode.
- a collecting bin for collecting the material removed from the rotatable electrode, such as powdered metal from the cathode, or organic waste from the anode.
- the electrolytic cell may be equipped with a device that has the property of breaking the liquid rise effect caused by the rotation movement of the rotatable electrode.
- a device that has the property of breaking the liquid rise effect caused by the rotation movement of the rotatable electrode.
- Such device referred to as a "meniscus-breaker”
- U tangential speed
- R rising
- the geometry and dimensions of the meniscus-breaker are determined from the following consideration : a) evolution of hydrogen, oxygen and other possible gases produced at the electrodes during the electrolysis process, b) liquid section above the meniscus-breaker that has to go down through the center hole of the device for being treated, c) presence of solid particles within that liquid (e.g. metallic powder). Because of these considerations, the bottom section of the meniscus-breaker must have a conical or pyramidal shape while the upper section must have an inverted similar shape on top of the bottom section, given an overall hour-glass shape.
- the angle present within both sections must be such that the bottom section allows the gases to exit upwardly toward the center hole of the meniscus-breaker (where the shaft of the rotatable electrode goes through) while the upper section allows the liquid charged with the solid particles (mostly metallic) to go back into the cell by gravity.
- the meniscus-breaker should be located below the nominal level of the of the liquid into the cell. Its rim (or borders) must closely touched the inner wall of the cell in such a manner that no liquid can go between the wall and the meniscus-breaker.
- the electrolytic cell may further comprise a collecting bin for collecting the material removed from the rotatable electrode, such as powdered metal from the cathode, or organic waste from the anode.
- a collecting bin for collecting the material removed from the rotatable electrode, such as powdered metal from the cathode, or organic waste from the anode.
- the invention provides a method for electro winning metals comprising the steps of passing a solution containing a metal through an electrolytic cell having an anode and cathode, simultaneously applying a direct current to the solution between the anode and the cathode, so as to deposit the metal on the cathode as a metal powder, rotating the cathode during deposition, and directing ultrasonic energy toward the cathode in order to remove the powdered metal therefrom.
- the ultrasonic energy may be directed toward the cathode at intervals.
- the electrolytic cell can be equipped with an hollow rotatable electrode that can be refrigerated; thus, it can be used for the electroextraction of a metal such as gallium that has a low melting point, that is present into a high temperature electrolyte such as those found in the aluminum extraction industry (bauxite processes).
- a metal such as gallium that has a low melting point
- a high temperature electrolyte such as those found in the aluminum extraction industry (bauxite processes).
- the gallium powder that is being produced when the rotatable electrode is polarized cathodically is recovered without using ultrasonic energy, but rather by removing the cathode from the high temperature electrolyte and dipping it into another liquid, preferably water, at a temperature above the melting temperature of gallium.
- the powder melts down from the cathode and can be easily recovered under a solid metallic deposit when the liquid is cooled down below the melting point of gallium.
- the methods, equipments and chemicals used to refrigerate the hollow rotatable electrode are numerous : any combination of method, equipment and chemical that allows the refrigeration of the surface of the electrode may be applied.
- the invention provides a method for oxidizing organic compounds comprising the steps of passing a solution containing organic compounds through an electrolytic cell having an anode and cathode, simultaneously applying a direct current to the solution between the anode and the cathode, so as to oxidize the organic compounds at the anode, rotating the anode during oxidation, and directing ultrasonic energy toward the anode in order to clean its surface therefrom.
- the ultrasonic energy may be directed toward the cathode at intervals.
- the invention allows the recovery of metals from diluted electrolytes, more specifically from solutions where the total metal concentration ranges from 0 to 3000 ppm, preferably between 20 to 500 ppm.
- the invention also provides economical recovery of metals from such solutions because metals are obtained in a form of a powder which can be removed from a rotatable electrode without using a mechanical device, such as a blade, to remove it.
- the powdery metal deposit is easily removed from the rotatable electrode with the use of ultrasonic energy. Then the removed powder metal can be recovered using an appropriate filtration system. This separation is further simplified when the rotatable electrode is cathodic.
- the use of ultrasonic energy to remove deposit from the rotatable electrode cleans this latter at the same time, hence, almost eliminating the use of mineral acids or other toxic chemicals to condition its surface for further use.
- the ultrasonic device of the invention can also be used to clean the surface of the rotatable electrode from organic fouling when the rotatable electrode is polarized as an anode for electrooxidation, thus avoiding complex methods for cleaning its conductive surface.
- the equipment is designed such that the rotatable electrode can be raised. Thus can be inspected, cleaned or repaired at will.
- the invention allows one also to selectively purify concentrated electrolytes from undesired low concentration metallic contaminants present into them. Furthermore, the invention can also be used to destroy organic contaminants present in low concentration in inorganic or organic conductive electrolytes, by electrooxidation. The desired electrochemical reaction is achieved depending upon the induced polarity of the rotatable electrode.
- the invention is more adapted to recover metals from plating processes and mining processes, but can be applied to other types of industries such as metal finishing.
- the recovery of metals lowers the amount of generated waste when the apparatus is installed up-stream a wastewater system, thus, reducing the amount of sludge to dispose on land-fields.
- FIG. 1 is a high-level illustration of an electrolytic cell in accordance with the teachings of this invention.
- Figure 2 is a schematic cross-section of the cell cavity of the electrolytic cell of Figure 1 ;
- Figure 3 illustrates the electrolytic cell of Figure 1 in an industrial application.
- the apparatus provided by the invention may be used either for electrowinning metals or oxidizing organic compounds.
- the operation of the apparatus is selectively charged by changing the polarization of a rotatable electrode, as is described below.
- an electrolytic cell 10 has a cell housing 12.
- the cell housing 12 defines a cell cavity 14.
- the form of the housing 12 of the electrolytic cell 10 is not restricted, and may be composed of any suitable material so long as the housing is electrically insulated from the electrodes.
- the housing is cylindrical, although other shapes are possible. In this embodiment, it is shown to be funnel-shaped.
- a rectifier 16 provides the necessary current and voltage required between the anode and the cathode to produce the powdery deposit when the rotatable electrode is polarized cathodically or to oxidize organic contaminants when the rotatable electrode is polarized anodically.
- the current is supplied to the electrodes by electrical busbars 26, 28.
- At least two electrodes, namely a cathode and an anode, are connected to the cathode and anode busbars 26, 28, respectively.
- the rotatable electrode can be polarized as the cathode or as the anode.
- the rotatable electrode can also be called the working electrode, and the static electrode is called the counter-electrode.
- the housing 12 includes an inlet port 18 and flow passage 20 for feeding the solution to be treated from a storage tank (not shown) to the cell 10, and an outlet port 22 for removal of the solution, both being effected by a pump 24.
- a pump 24 When the powder is being deposited as a result of the electrochemical reaction the solution will be depleted of metal or organic contaminant.
- the depleted solution is passed through a tank 32 containing filter 52 to a wastewater facility. In the case of a solution containing copper, it is found that even during the deposition stage some powder becomes dislodged and is entrained with the depleted solution to the filter 52.
- the current Periodically the current is switched off and ultrasonic energy is applied to the electrode to dislodge the powder. Typically the current may be stopped for anywhere from one to four minutes every 24 - 36 hours. Typically during the dislodgement phase the speed of rotation of the rotatable electrode is reduced by 25%.
- the dislodged powder is entrained in the liquid flowing through the outlet and subsequently passed through the filter 52 for removal. Since the liquid flowing through the cell in this phase is not depleted, the resulting liquid, after flowing through the tank 32, is switched to a buffer tank (not showns) rather than the wastewater facility. The liquid in the buffer tank can be subsequently returned to the cell for further processing during a subsequent deposition stage.
- the cell 10 also includes an ultrasound generator having an oscillator 30 and ultrasound transducers 31 for directing ultrasonic energy at the rotatable electrode during the powder removal phase.
- the rotatable electrode 40 is a distinct discrete component separate from the housing mounted on a drive shaft 60.
- the rotatable electrode 40 is shown as being drum-shaped with a concentric fixed cylindrical counter electrode 42.
- the precise form of the rotatable electrode 40 depends on the metal or organic contaminant to be recovered.
- the rotatable electrode 40 may be frustoconical, with its larger radius end uppermost, that is towards the circular upper opening of the electrolytic cell.
- the rotatable electrode may be in the shape of a V with an opening at the bottom and a wide opening at the top.
- the rotatable electrode may comprise two face plates and a spacer member therebetween.
- the rotatable electrode is an integral structure comprising a carrier sheet with a conductive element at least on one side, which is conveniently of metal.
- the rotatable electrode 40 may be a hollow disk. Such a shape has a simple mechanical construction.
- the rotatable electrode may be formed from a generally flat sheet of flexible material with an electrically conductive surface on one major face thereof, and an electrically non-conductive surface on a portion of the other major face thereof, and securing means to enable the sheet to be folded and secured in place.
- Suitable conductive materials include stainless steel, titanium and its alloy aluminum, or any other conductive material.
- the counter-electrode 42 is also situated within the cell cavity 14.
- the material of the counter-electrode 42 is not limited in any particular way and may be selected from any material typically used in the art. Usable materials may include stainless steel, platinized titanium, lead or graphite, among others.
- the working electrode is the one that rotates.
- the rotatable electrode is the electrode where the target reaction occurs.
- the rotatable electrode can therefore be polarized cathodically or anodically.
- each of the electrodes 40, 42 and electrolytic cell 10 should all correspond with one another.
- the anode is in the shape of a rod, its axis will coincide with the axis of the electrolytic cell, where this is also in cylindrical form.
- the cell may be tubular wherein if the cathode is cylindrical, it surrounds the cylindrical anode.
- the cell may be box-shaped and divided into a cathode compartment and an anode compartment by a diaphragm.
- the cell is cylindrical, and the anode and cathode are both cylindrical and in spaced relationship to one another.
- the source 16 of direct electrical current is connected between the anode and cathode via leads 26, 28 to allow current to flow.
- the rotatable electrode When the rotatable electrode is polarized cathodically, metal ions in solution in the cavity migrate toward the cathode where the metal is deposited. Therefore, the cathode rotates to improve the mass transport and reduce the thickness of the diffusion layer.
- the cathode is rotated by means such as one rotating shaft which may be made of the same metal as the cathode, through which the electric current is fed and which rotate in two bearings formed in walls of the cell. Rotation of the cathode can be achieved by means of an electric motor (not shown) through a speed controller (not shown).
- the rotatable electrode 40 is shown to rotate clockwise, the direction of rotation may also be counter-clockwise.
- rotatable electrode 40 When more than one rotatable electrode 40 is used to treat a certain volume of solution, they can be connected in parallel or in series in order to achieve the desired contamination level of the solution to be treated. Each rotatable electrode40 can operate under similar or different operation modes.
- Figure 3 illustrates the electrolytic cell of Figure 1 in an industrial application.
- Solution from storage tank 50 is pumped into the cell 10 for processing by means of pump 54.
- the cell is fitted with an ultrasonic level detector that controls the operation of pumps 24, 54 to maintain the liquid in the cell at the desired level.
- the filter 52 can include filter bags arranged such that the liquid flows through their walls and deposits the powder within the bags for subsequent removal. Any suitable filter technology can be employed for this purpose.
- the busbar 26 is electrically connected to the rotatable electrode 40 by means of a brush connector 62 in contact with the shaft 60.
- the shaft 60 is driven in rotation by a motor 64 and pulley system 66.
- the shaft rotates in bearings 68.
- the electrolytic cell may preferably be equipped with a device 27 referred to as a "meniscus breaker that eliminates the meniscus rising effect that occurs when the tangential speed is higher than about lm/sec.
- the device 27 has a "Chinese hat” shape, that is it is in the form of a disk with a central aperture 27a, the disk having upper and lower surfaces 27b tapering inwardly toward the central aperture 27a. This device prevents the meniscus from rising up the cell while permitting gases formed within the cell to escape.
- a cathode and anode are put into the cell 10.
- the inlet port is connected to the storage tank holding solution to treat, and the solution is pumped via a pump from the tank into the cell cavity to fill the cavity and close the circuit between the cathode and anode.
- the vast majority of expected applications are in aqueous media, but in certain cases it could be in non-aqueous solutions or electrolytes (e.g. ethanol, benzoic acid, etc.).
- electrolytes e.g. ethanol, benzoic acid, etc.
- enough solution is pumped into the cavity to completely submerge both the cathode and the anode.
- the solution is suitably pumped into the cell cavity.
- the total metal concentration of the solution is from 0 to 3000 ppm (mg/L), preferably between 20 to 500 ppm (mg/L).
- the cell can be supplied with any form of electric current, such as direct current, alternating current, pulsed, periodic reverse pulse, etc.
- the anode and cathode of the electrolytic cell are connected to a rectifier which controls the application of electrical power to the anode and cathode.
- the apparatus of this invention can be used to produce metal powders when the rotatable electrode is cathodically polarized. Powders may include metals or alloys in pure forms or metallic hydroxides or oxides. The definition of a powder shall be broad (grain size, shape, metal ceramic, metal, alloys etc.). The formation of a powder, instead of a compact film of metal or alloy, allows the use of ultrasounds to remove to metal from the cathode (as is described below).
- Deposition of metal powder is accomplished by the rigid control of process parameters.
- the parameters to be controlled include: voltage, current density (pushed toward the limiting current) at the cathode, plating time, cathode rotation speed, electrolytic conditions through proper adjustments of pH, composition, temperature, conductivity, viscosity, concentration, and other parameters to ensure the metal precipitates on the cathode (being reduced) as a powder.
- the voltage and current are selected by fixing the current level across the electrodes at an optimum level for the range of concentrations found in a particular application. This current level has been determined by experimentation, and is present depending upon the particular use of the apparatus when the apparatus is installed.
- Electrowinning conditions are determined on a case by case basis.
- the metal powder produced at the cathode may be removed periodically by switching off the current and applying ultrasonic energy.
- the metal deposit removal period may vary from one electrolyte to another.
- the deposit does not exceed 10% of the distance between anode and cathode.
- the preferred gap between electrodes is 2 cm, thus, a 0.2 cm thick deposit will be removed by using the ultrasonic device.
- Powder removal conditions can vary from one case to another. For instance, powder can be removed as per determined numbers of coulombs or thickness, depending upon powder properties and electrolyte composition.
- the ultrasonic generator 30 supplies an alternating-current energy at an excitation frequency in an ultrasonic range, for example, from 16kHz to 40 kHz, 25 kHz being preferred.
- the ultrasonic electrical energy is converted into ultrasonic mechanical vibrations at a frequency corresponding to the excitation frequency.
- the mechanical vibrations produced by the transducers 31 are applied directly toward the cathode to cause cavitation at the surface of the cathode. This effect causes the metal powder to be removed from the electrode surface. For example, to remove a zinc powder deposit from the rotatable electrode, 2 to 4 minutes of 20% intense ultrasounds at 25 kHz every 24 hours of deposition is sufficient to loosen the powder from the rotatable electrode. The loosened power deposit is subsequently collected by the filter 52.
- two ultrasonic transducers 31 placed at 180 degrees from one another are installed (as seen in Figure 1).
- the width of the facing plate of the vibrators is half its height, this latter being equal to the height of the rotatable electrode.
- the metal becomes deposited as discrete particles at the cathode and is collected at the bottom of the cell, which is preferably conical or shaped as a funnel having a practical solid angle from 20 to 75 degrees, 45 degrees being preferred, or as a loosely adherent deposit which may be lifted from the cell and washed off the cathode.
- the metal powder accumulated at the bottom of the cavity can be removed periodically or continuously through the bottom outlet on removal of a plug or through a valve.
- a collecting bin is located at the bottom of the cell, and collects the powdered metal removed from the cathode.
- the powder can be collected either by recovering metals from industrial process waters (plating shops, smelters, mining, etc.) and by producing a specific powder from a defined electrolyte.
- Electrolyte composition can be such that metal powder can be made of a pure metal or alloys.
- the apparatus of this invention may also be used to oxidize organic compounds when the rotatable electrode is anodically polarized.
- the rotatable electrode is capable of destroying organic contaminants from organic or inorganic electrolytes. If fouling of the rotatable electrode occurs during such application, ultrasonic cleaning is performed using the ultrasonic generators.
- phenol or creosols can be electrooxidized from 1500 ppb ( ⁇ g/L) down to 20 ppb ( ⁇ g L) using a rotatable electrode
- the nature of the organic compounds to be destroyed, its concentration, and the material to use as electrodes such as anode and cathode are not limited.
- the rotatable electrode is most efficient in destroying organic compounds found in low concentrations in organic or aqueous solutions.
- the outlet port is connected to the original tank in a closed loop fashion or to another tank for further use or disposal of the solution.
- the treated solution may go directly into the sewer. Otherwise, the treated solution may be connected to a conventional wastewater system (or returned to the process).
- the flow rate of the liquid being treated is such that the volume of the liquid that enters the inlet is the same than the one that comes out of the outlet.
- the cell can be employed repeatedly with the same anode and cathode.
- a solution containing 100 ppm of zinc from a zinc chloride plating solution is reduced to 15 ppm in two steps: the first step uses a current density of 80 mA/cm at a rotatable electrode whose tangential speed is 3.5 - 4.5 m/sec with a treatment time 1.33 times the flow rate; and the second uses half the current density of the first step but twice the time of treatment.
- a solution containing 200 ppm of copper from an acid copper plating solution is reduced to 20 ppm with a current density of 60 mA/cm at a rotatable electrode with a tangential speed of 3.0 - 4.0 m sec with a treatment time equal to 1.25 times the flow rate.
- a solution containing 200 ppm of nickel from an acid nickel sulfamate plating solution is reduced to 30 ppm with a current density of 27 mA/cm 2 at a rotatable electrode with a tangential speed of 2.5 - 3.5 m/sec with a treatment time equal to 1.50 times the flow rate.
- a solution containing 200 ppm of tin from an acid tin chloride plating solution is reduced to 30 ppm with a current density of 40 mA/cm2 at a rotatable electrode with a tangential speed of 3.0 - 3.5 m sec with a treatment time equal to 1.15 times the flow rate.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Electrolytic Production Of Metals (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US50295003P | 2003-09-16 | 2003-09-16 | |
PCT/CA2004/001686 WO2005026412A1 (en) | 2003-09-16 | 2004-09-16 | An electrolytic cell for removal of material from a solution |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1680530A1 EP1680530A1 (en) | 2006-07-19 |
EP1680530A4 true EP1680530A4 (en) | 2007-06-13 |
Family
ID=34312428
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04761844A Pending EP1680530A4 (en) | 2003-09-16 | 2004-09-16 | ELECTROLYTIC CELL INTENDED TO REMOVE A MATERIAL FROM A SOLUTION |
Country Status (9)
Country | Link |
---|---|
US (1) | US20050183947A1 (pt) |
EP (1) | EP1680530A4 (pt) |
KR (1) | KR20060067973A (pt) |
CN (1) | CN1875132A (pt) |
AU (1) | AU2004272647A1 (pt) |
BR (1) | BRPI0414384A (pt) |
CA (1) | CA2539161A1 (pt) |
WO (1) | WO2005026412A1 (pt) |
ZA (1) | ZA200603046B (pt) |
Families Citing this family (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2525018C (en) * | 2004-11-04 | 2009-10-06 | Raul Nibaldo Ibarra Macaya | Electrolytic cell or modified electrolytic cell for the metal recovery its base or floor comprising pyramid-shaped funnels which allow the continuous extraction of sludge from thebottom of the cell, in addition discloses the method to recover the sludge |
WO2007124605A1 (en) * | 2006-05-03 | 2007-11-08 | Global Ionix | Electrolytic cell comprising means for dislodging electrolytic deposits from an electrode |
CN101363126B (zh) * | 2008-09-05 | 2011-11-23 | 江苏技术师范学院 | 制备纳米级金属粉体的装置 |
KR20140068871A (ko) * | 2011-07-08 | 2014-06-09 | 인스티튜트 오브 케미컬 테크놀로지 (딤드 유니버시티) | 씨유 씨엘 열화학 사이클을 사용하는 수소의 생산에 사용되는 전기화학 전지 |
US9221081B1 (en) | 2011-08-01 | 2015-12-29 | Novellus Systems, Inc. | Automated cleaning of wafer plating assembly |
US9988734B2 (en) | 2011-08-15 | 2018-06-05 | Lam Research Corporation | Lipseals and contact elements for semiconductor electroplating apparatuses |
US10066311B2 (en) | 2011-08-15 | 2018-09-04 | Lam Research Corporation | Multi-contact lipseals and associated electroplating methods |
US9228270B2 (en) | 2011-08-15 | 2016-01-05 | Novellus Systems, Inc. | Lipseals and contact elements for semiconductor electroplating apparatuses |
CN104010974B (zh) * | 2011-12-29 | 2016-09-21 | 大金工业株式会社 | 净化装置 |
SG11201406133WA (en) * | 2012-03-28 | 2014-10-30 | Novellus Systems Inc | Methods and apparatuses for cleaning electroplating substrate holders |
TWI609100B (zh) | 2012-03-30 | 2017-12-21 | 諾發系統有限公司 | 使用反向電流除鍍以清洗電鍍基板夾持具 |
US9746427B2 (en) | 2013-02-15 | 2017-08-29 | Novellus Systems, Inc. | Detection of plating on wafer holding apparatus |
US10416092B2 (en) | 2013-02-15 | 2019-09-17 | Lam Research Corporation | Remote detection of plating on wafer holding apparatus |
KR101444672B1 (ko) * | 2014-01-13 | 2014-09-26 | 영남대학교 산학협력단 | 금속 함유 슬러지의 자원화설비 |
CN103911631B (zh) * | 2014-04-01 | 2016-06-08 | 攀钢集团攀枝花钢铁研究院有限公司 | 收集熔盐电解阴极产物的装置及熔盐电解系统 |
CN104357881B (zh) * | 2014-11-21 | 2017-11-28 | 刘晓鹏 | 一种基于全密封选择性粉体电解装置的电解系统 |
KR101719575B1 (ko) * | 2015-06-10 | 2017-03-24 | 한국기계연구원 | 나노 입자를 위한 제조장치 및 양자점 제조방법 |
US10053793B2 (en) | 2015-07-09 | 2018-08-21 | Lam Research Corporation | Integrated elastomeric lipseal and cup bottom for reducing wafer sticking |
CN105506668B (zh) * | 2015-12-23 | 2017-08-29 | 四川省银河化学股份有限公司 | 一种萘醌残液的电解综合利用方法 |
CN105621538A (zh) * | 2016-03-11 | 2016-06-01 | 上海丁香环境科技有限公司 | 旋转电极式水处理装置 |
EP3257818A1 (en) | 2016-06-15 | 2017-12-20 | Aquatec, Proyectos Para El Sector Del Agua, S.A.U. | A method and system for electrochemically purifying water |
CN106498447B (zh) * | 2016-11-23 | 2018-10-19 | 北京建筑大学 | 金属有机骨架材料的批量电化学合成装置及方法 |
CN106554090A (zh) * | 2017-01-16 | 2017-04-05 | 沈阳瀚威科技有限公司 | 一种循环水电解自动除垢装置及方法 |
CN107935257B (zh) * | 2017-12-28 | 2021-05-25 | 贵州鹤庭沃德环境工程有限公司 | 一种净水器 |
KR102300421B1 (ko) * | 2019-08-09 | 2021-09-13 | 한국에너지기술연구원 | 입자상 물질 고정형 회전전극을 적용한 저전위도금 장치 |
CN113622011B (zh) * | 2021-08-03 | 2022-09-27 | 天津科技大学 | 一种制备多孔阳极氧化铝膜的工艺方法和装置 |
CN116445985B (zh) * | 2023-03-29 | 2023-10-27 | 扬州新达再生资源科技有限公司 | 镀锌槽浮渣高回收率再生节能锌粉制备工艺 |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU893886A1 (ru) * | 1980-04-25 | 1981-12-30 | Кировский Политехнический Институт | Электролизер дл очистки сточной воды |
GB2093067A (en) * | 1981-02-13 | 1982-08-25 | Nat Res Dev | Removing electro-deposit from rotating cylindrical electrode |
Family Cites Families (57)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2053222A (en) * | 1930-09-26 | 1936-09-01 | James H Lucas | Apparatus for producing metallic powders |
US3154296A (en) * | 1961-01-25 | 1964-10-27 | Leslie L Balassa | Foam arrestor for mixing machine |
US3156248A (en) * | 1962-03-20 | 1964-11-10 | Dow Chemical Co | Cleaning apparatus |
US3301777A (en) * | 1963-04-01 | 1967-01-31 | American Potash & Chem Corp | Anode for the electrowinning of manganese |
US3414486A (en) * | 1966-02-18 | 1968-12-03 | Esb Inc | Method for producing flakes of nickel |
US3616277A (en) * | 1968-07-26 | 1971-10-26 | Kennecott Copper Corp | Method for the electrodeposition of copper powder |
US3533887A (en) * | 1968-10-21 | 1970-10-13 | Bunker Hill Co | Rapping device that alternately impacts cathode sheets along the bottom edge during hydraulic stripping operations |
US3654115A (en) * | 1968-12-30 | 1972-04-04 | Texas Instruments Inc | Manufacture of perforated metal foil |
US3840032A (en) * | 1969-10-25 | 1974-10-08 | Asturiana De Zinc Sa | Hydraulic apparatus for removing the zinc deposited on zinc electrolysis cathodes |
US3830710A (en) * | 1971-01-08 | 1974-08-20 | Int Nickel Co | Masked electrode structure and process for electrolytic deposition of metals |
DE2349286C3 (de) * | 1973-10-01 | 1982-11-18 | Götz, Friedrich, Dipl.-Phys., 5628 Heiligenhaus | Vielfachelektrolysezelle zur Erzeugung eines Gemisches von Wasserstoff und Sauerstoff |
US3866068A (en) * | 1974-03-20 | 1975-02-11 | Lewis Corp | Frequency varying oscillator circuit vibratory cleaning apparatus |
US4028199A (en) * | 1974-08-05 | 1977-06-07 | National Development Research Corporation | Method of producing metal powder |
US4039422A (en) * | 1975-10-14 | 1977-08-02 | Packer Elliot L | Metal recovery unit |
US4040915A (en) * | 1976-06-15 | 1977-08-09 | The International Nickel Company, Inc. | Method for producing regular electronickel or S nickel rounds from electroplating baths giving highly stressed deposits |
DE2739970A1 (de) * | 1976-09-10 | 1978-03-16 | Pour La Recuperation Electroly | Verfahren zur rueckgewinnung des zinks aus dieses enthaltenden rueckstaenden, und bei diesem verfahren benutzbare elektrolysevorrichtung |
JPS5817269B2 (ja) * | 1976-12-17 | 1983-04-06 | ソニー株式会社 | チタン又はチタン合金の電着法 |
US4147597A (en) * | 1978-02-21 | 1979-04-03 | The International Nickel Company, Inc. | Method for producing electrolytic nickel in particulate forms under condition of high and variable internal stress |
US4234333A (en) * | 1979-04-25 | 1980-11-18 | Fansteel, Inc. | Process for recovering metal carbide powder from cemented carbides |
US4242190A (en) * | 1979-05-29 | 1980-12-30 | King Arthur S | Rotary electrodic treater with jet action cleaning |
ATE17875T1 (de) * | 1980-10-27 | 1986-02-15 | Conradty Nuernberg | Elektrode fuer schmelzflusselektrolyse. |
US4406752A (en) * | 1981-11-12 | 1983-09-27 | General Electric Company | Electrowinning of noble metals |
US4406753A (en) * | 1982-01-19 | 1983-09-27 | Ciba-Geigy Ag | Electrolytic metal recovery cell and operation thereof |
US4432840A (en) * | 1982-04-26 | 1984-02-21 | Formosa Plastics Corporation | Prevention of polymer buildup in polymerization reactors using thin organic coatings by electrolysis of phenol |
KR920002415B1 (ko) * | 1984-02-27 | 1992-03-23 | 씨. 피. 케미칼스 인코포레이티드 | 금속 전해 회수 방법 |
JPS6110496A (ja) * | 1984-06-26 | 1986-01-17 | タマリスリ−ダイメンシヨナルドロ−イング有限会社 | 透視図作成装置 |
JPS61106788A (ja) * | 1984-10-29 | 1986-05-24 | Toppan Printing Co Ltd | 金属回収方法およびその装置 |
US4675085A (en) * | 1985-07-31 | 1987-06-23 | Adalberto Vasquez | Method and apparatus for recovery of metal from solution |
US4647345A (en) * | 1986-06-05 | 1987-03-03 | Olin Corporation | Metallurgical structure control of electrodeposits using ultrasonic agitation |
JPH0795474B2 (ja) * | 1987-03-17 | 1995-10-11 | 日本カ−ボン株式会社 | 電気ア−ク製鋼等金属の溶解および精錬法ならびにそれに供する電極冷却装置 |
FR2616810B1 (fr) * | 1987-03-25 | 1989-08-18 | Rhone Poulenc Sante | Procede electrochimique pour recuperer le rhodium metallique a partir de solutions aqueuses de catalyseurs usages |
DE3832674A1 (de) * | 1988-09-27 | 1990-03-29 | Kodak Ag | Metallrueckgewinnungs-vorrichtung |
US5089097A (en) * | 1989-03-17 | 1992-02-18 | Konica Corporation | Electrolytic method for recovering silver from waste photographic processing solutions |
US5228976A (en) * | 1990-07-09 | 1993-07-20 | At&T Bell Laboratories | Hydrodynamically modulated hull cell |
US5250166A (en) * | 1990-09-21 | 1993-10-05 | Doryokuro Kakunenryo Kaihatsu Jigyodan | Method of recovering palladium by electrolysis and apparatus therefor |
JPH04157192A (ja) * | 1990-10-19 | 1992-05-29 | Fuji Photo Film Co Ltd | 銀回収装置 |
TW197534B (pt) * | 1991-03-21 | 1993-01-01 | Eltech Systems Corp | |
DE4123196A1 (de) * | 1991-07-12 | 1993-01-14 | Heraeus Elektrochemie | Elektrode fuer das austragen von metallen aus metallionen enthaltender loesung |
CA2060264C (en) * | 1992-01-29 | 2004-04-20 | Philippe Ferron | Electrolytic cell |
CA2082531A1 (en) * | 1992-11-10 | 1994-05-11 | George Houlachi | Production of compact zinc deposits from alkaline electrolyte |
US5360525A (en) * | 1993-03-16 | 1994-11-01 | United Foils Inc. | Apparatus for making metal foil |
US5409594A (en) * | 1993-11-23 | 1995-04-25 | Dynamotive Corporation | Ultrasonic agitator |
DE4428787C2 (de) * | 1994-08-13 | 1997-05-07 | Fraunhofer Ges Forschung | Verfahren und Vorrichtung zum Reinigen von Abwasser |
US5454924A (en) * | 1994-09-09 | 1995-10-03 | Agfa-Gevaert N.V. | Apparatus for the electrolytic recovery of silver from solutions containing silver |
US5753099A (en) * | 1996-04-03 | 1998-05-19 | Metafix Inc. | Metal recovery |
US5653860A (en) * | 1996-05-02 | 1997-08-05 | Mitsubishi Semiconductor America, Inc. | System for ultrasonic removal of air bubbles from the surface of an electroplated article |
CA2256929C (en) * | 1997-12-28 | 2008-02-12 | Kemix (Proprietary) Limited | Electrowinning cell |
US6258247B1 (en) * | 1998-02-11 | 2001-07-10 | Northwest Aluminum Technology | Bath for electrolytic reduction of alumina and method therefor |
AU4822499A (en) * | 1998-06-15 | 2000-01-05 | Boeing Company, The | Making particulates of controlled dimensions |
US6447664B1 (en) * | 1999-01-08 | 2002-09-10 | Scimed Life Systems, Inc. | Methods for coating metallic articles |
EP1165862A1 (en) * | 1999-01-21 | 2002-01-02 | GA-TEK Inc. | Process for recovering copper from a high acid mixed metal solution |
JP2001081590A (ja) * | 1999-09-10 | 2001-03-27 | Mitsui Mining & Smelting Co Ltd | 銅の高電流密度電解法 |
CA2329553A1 (en) * | 1999-12-22 | 2001-06-22 | Yves Michel Henuset | An electrochemical cell and process for reducing the amount of organic contaminants in metal plating baths |
US6827832B2 (en) * | 1999-12-22 | 2004-12-07 | National Research Council Of Canada | Electrochemical cell and process for reducing the amount of organic contaminants in metal plating baths |
US6589298B1 (en) * | 2000-05-26 | 2003-07-08 | Integran Technologies, Inc. | Surface treatment of metallic components of electrochemical cells for improved adhesion and corrosion resistance |
DE10112075C1 (de) * | 2001-03-12 | 2002-10-31 | Eilenburger Elektrolyse & Umwelttechnik Gmbh | Verfahren und Vorrichtung zur Rückgewinnung von Metallen, auch in Kombination mit anodischen Koppelprozessen |
US6517701B1 (en) * | 2001-08-14 | 2003-02-11 | Centaur Mining Exploration Ltd. | Lead, zinc and manganese recovery from aqueous solutions |
-
2004
- 2004-09-16 AU AU2004272647A patent/AU2004272647A1/en not_active Abandoned
- 2004-09-16 EP EP04761844A patent/EP1680530A4/en active Pending
- 2004-09-16 KR KR1020067007414A patent/KR20060067973A/ko not_active Application Discontinuation
- 2004-09-16 WO PCT/CA2004/001686 patent/WO2005026412A1/en active Search and Examination
- 2004-09-16 CA CA002539161A patent/CA2539161A1/en not_active Abandoned
- 2004-09-16 US US10/941,900 patent/US20050183947A1/en not_active Abandoned
- 2004-09-16 BR BRPI0414384-1A patent/BRPI0414384A/pt not_active IP Right Cessation
- 2004-09-16 CN CNA2004800316598A patent/CN1875132A/zh active Pending
-
2006
- 2006-04-13 ZA ZA200603046A patent/ZA200603046B/xx unknown
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
SU893886A1 (ru) * | 1980-04-25 | 1981-12-30 | Кировский Политехнический Институт | Электролизер дл очистки сточной воды |
GB2093067A (en) * | 1981-02-13 | 1982-08-25 | Nat Res Dev | Removing electro-deposit from rotating cylindrical electrode |
Non-Patent Citations (2)
Title |
---|
DATABASE WPI Week 198244, Derwent World Patents Index; AN 1982-94507E, XP002431886 * |
See also references of WO2005026412A1 * |
Also Published As
Publication number | Publication date |
---|---|
US20050183947A1 (en) | 2005-08-25 |
CA2539161A1 (en) | 2005-03-24 |
WO2005026412A1 (en) | 2005-03-24 |
EP1680530A1 (en) | 2006-07-19 |
AU2004272647A1 (en) | 2005-03-24 |
ZA200603046B (en) | 2007-09-26 |
CN1875132A (zh) | 2006-12-06 |
KR20060067973A (ko) | 2006-06-20 |
BRPI0414384A (pt) | 2006-11-21 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US20050183947A1 (en) | Electrolytic cell for removal of material from a solution | |
US20060243595A1 (en) | Electrolytic cell for removal of material from a solution | |
US5558755A (en) | Method for removing contaminants from an aqueous medium | |
US20080223731A1 (en) | Advanced Electro-Coagulation Device And Process Of Using The Same For Wastewater Treatment | |
CN203498138U (zh) | 平行多级电化学水处理设备 | |
KR20090038445A (ko) | 연수화 방법과 그 장치 | |
US6179991B1 (en) | Machine and process for treating contaminated water | |
CN204400672U (zh) | 导流口错位的多级电化学水处理设备 | |
CN203498136U (zh) | 渐进三级电化学水处理设备 | |
EP0769475B1 (en) | Process and apparatus for deactivation or destruction of microorganisms by an electric charge and vibration | |
US20050279626A1 (en) | Wastewater treatment equipment | |
CN113165917B (zh) | 用于通过电凝聚处理废水的电极电解池的清洁方法和装置 | |
KR20090031483A (ko) | 재생성 전해 연마 제염과 전기 흡착 및 증착을 이용한제염폐액 처리 | |
JPS6338435B2 (pt) | ||
KR20150135158A (ko) | 폐수로부터 금속의 추출 및 회수 처리장치 | |
CN203498137U (zh) | 渐进四级电化学水处理设备 | |
JPS5919994B2 (ja) | 金属の稀薄溶液から金属粉末を製造する方法 | |
JP4438570B2 (ja) | スケール回収装置 | |
SU893886A1 (ru) | Электролизер дл очистки сточной воды | |
JP2009166176A (ja) | 水溶性クーラント浄化装置 | |
JPH1085754A (ja) | 微小油滴分離用電解槽及び微小油滴分離方法 | |
RU2221754C2 (ru) | Способ и устройство для электровыделения тяжелых металлов из технологических растворов и сточных вод | |
JP3469134B2 (ja) | 電気化学方式によるエマルジョン中の金属微粒子の除去装置及び除去方法 | |
CN1041578A (zh) | 净化液体介质用的电解装置 | |
CN1039570A (zh) | 污水净化电解槽 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20060407 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR |
|
DAX | Request for extension of the european patent (deleted) | ||
A4 | Supplementary search report drawn up and despatched |
Effective date: 20070514 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |