Method and device for removing soluble impurities

Abstract

A method and apparatus for removing soluble impurities, the method comprising the following steps: (1) establishing an electrolytic bath (1), at least one electrode (2, 3) in the electrolytic bath (1) being wrapped by a filter bag (4), the bottom of the filter bag (4) at least partially leaving the bottom surface of the electrolytic bath; a vibrator (6) capable of enabling the filter bags to vibrate and a liquid suction pipe (5) communicated to the outside of the electrolytic bath are arranged, a liquid suction port of the liquid suction pipe (5) is formed in the filter bags (4), and at least one liquid suction port is formed in each filter bag (4); (2) filling a washing solution (28) and a solid washed substance (24) with soluble impurities in an area outside the filter bag (4) in the electrolytic bath (1), and dissolving the soluble impurities in the washing solution (28) to form impurity ions; (3) starting an electrolysis power supply to ionize foreign ions, and extracting the foreign ions gathered near the electrodes (2 and 3) through a liquid suction pipe (5) for discharging and / or electrolyzing the foreign ions into gas for electro-precipitation removal; the vibrator (6) is continuously or intermittently started; and (4) after the impurity removal process is completed, solid substances in the electrolytic cell are taken out through solid-liquid separation.

Description

A method and device for removing soluble impurities Technical Field

[0001] The present invention belongs to the technical field of chemical purification, and in particular relates to a method and a device for removing soluble impurities. Background Art

[0002] In current industrial production, washing is often required to remove water-soluble electrolyte impurities from chemical products to ensure that they meet market requirements. For example, washing can be used to purify products such as sodium sulfate from ferrous hydroxide, sodium chloride from basic copper carbonate, hydrochloric acid, sodium chloride, and ammonium chloride from copper oxalate, and sodium chloride from copper oxide. Existing chemical product washing methods involve conventional water washing, where the chemical product is washed repeatedly with water until it meets the required standards. This process and the required equipment are simple, making it widely adopted. However, conventional water washing methods require large amounts of fresh water for multiple washes, with the total water consumption often being tens or even hundreds of times the weight of the material being washed. Although most cleaning wastewater has low impurity concentrations and can be discharged directly, the earth's freshwater resources are limited, and global industrialization has also resulted in a large amount of conventional water washing wastewater. The discharge of this large amount of conventional water washing process wastewater still causes environmental pollution.

[0003] Therefore, the applicant proposed a method for separating electrolyte impurities from water-insoluble compounds in the Chinese patent application No. 202310528764.7, which updated and improved the washing and purification process of chemical products. This method uses a separator to enclose a cleaning tank area in the electrolytic cell and confines the water-insoluble compounds (i.e., the chemical products to be washed) therein. The electric field force generated by the electrolytic anode and the electrolytic cathode after energization causes the cations and anions in the washing liquid in the cleaning tank area to migrate away from the cleaning tank area, thereby reducing the total ion concentration of the washing liquid in the cleaning tank area and promoting the separation of electrolyte impurities from the water-insoluble compounds. This achieves a better effect of removing electrolyte impurities when the amount of washing liquid used is the same. However, in this method, the washed chemicals are placed in the cleaning tank area enclosed by the separator, and the solid washed chemicals are accumulated at the bottom due to gravity. Therefore, they are easily in close contact with the separator over a large area, which easily leads to clogging of the separator and reduces the efficiency of separating electrolyte impurities. Therefore, there is still a need for further improvements to the washing process and device for chemical products.

[0004] Summary of the Invention

[0005] The first object of the present invention is to provide a method for removing soluble impurities, thereby improving the washing and purification process of solid chemicals, thereby increasing purification efficiency and saving water. The second object is to provide an apparatus for removing soluble impurities using the above method.

[0006] A method for removing soluble impurities comprises the following steps:

[0007] (1) establishing an electrolytic cell, wherein at least one electrode in the electrolytic cell is wrapped by a filter bag, the bottom of the filter bag is at least partially away from the bottom surface of the electrolytic cell, and the electrode is an electrolytic anode and / or an electrolytic cathode;

[0008] In the electrolytic cell, the electrolytic anode is connected to the positive electrode of the electrolytic power supply, and the electrolytic cathode is connected to the negative electrode of the electrolytic power supply;

[0009] A vibrator capable of vibrating the filter bag and a liquid suction pipe connected to the outside of the electrolytic cell are provided, wherein the liquid suction port of the liquid suction pipe is provided in the filter bag and each filter bag has at least one liquid suction port;

[0010] (2) The area outside the filter bag in the electrolytic cell is filled with a washing liquid and a solid material to be washed containing soluble impurities to form a solid-liquid mixture, so that the soluble impurities dissolve in the washing liquid to form impurity ions, and the electrolytic anode and the electrolytic cathode are immersed in the washing liquid;

[0011] (3) Turn on the electrolysis power supply to ionize the impurity ions, and extract the impurity ions gathered near the electrode through the pipette to remove the solution and / or convert them into gas through electrolysis for removal; the vibrator is started continuously or intermittently to shake off the washed matter adhering to the filter bag;

[0012] (4) When the concentration of impurity ions in the washing liquid in the electrolytic cell reaches or is lower than the concentration standard set by the process requirements, the impurity removal process of the washed material is completed, and then the solid matter in the electrolytic cell is removed by solid-liquid separation to obtain the washed and purified product.

[0013] In step (4), the impurity ion concentration in the washing liquid in the electrolytic cell reaches or is lower than the concentration standard set by the process requirements, which is equivalent to the impurity ion content of the washed material reaching the set standard.

[0014] In the present invention, a single filter bag wraps one electrolytic anode or electrolytic cathode, or wraps more than one electrolytic anode or electrolytic cathode at the same time, or wraps at least one electrolytic anode and at least one electrolytic cathode at the same time.

[0015] The pipette is used to absorb and discharge the solution enriched with impurity ions around the electrode.

[0016] The filter bag is used to effectively prevent solid washed material outside the filter bag from entering the electrolytic cell, thereby preventing the washed material from contacting the electrodes and initiating electrochemical reactions, or preventing the washed material from being sucked away in large quantities along with the washing liquid by the pipette. The bottom of the filter bag is at least partially separated from the bottom surface of the electrolytic cell, thereby leaving space below the filter bag and utilizing the gravity of the washed material to prevent it from coming into close contact with the filter bag over a large area. The vibrator can vibrate the filter bag, providing vibrational kinetic energy to the filter bag and / or the solution near the filter bag to shake off washed material adhering to the filter bag, thereby preventing clogging of the filter bag and facilitating the smooth migration of impurity ions through the filter bag under the action of the electric field force and their accumulation around the electrically attracted electrodes. The combined effect of the above technical features ionizes and removes impurities from the washed material, effectively preventing the washed material from clogging the filter bag and affecting the removal of soluble impurities, and improving the efficiency of purification.

[0017] Preferably, the filter bag is made of a material that is insoluble in the solid-liquid mixture of the material being cleaned and the cleaning solution, and at least one surface of the bag is made of a material that effectively blocks solid material from entering the bag while allowing water and ions to pass through. Examples include an anion exchange membrane, a cation exchange membrane, a non-ion-selective membrane, a reverse osmosis membrane, and a solid filtration medium. Preferably, the filter bag is made of at least one of filter cloth, filter plate, and filter screen, avoiding the use of expensive ion exchange membranes that increase production equipment costs.

[0018] The washed substance described in the present invention is a solid substance that is insoluble or slightly soluble in the washing liquid and contains impurities that are soluble in the washing liquid. These impurities can dissolve directly in the washing liquid or react with components in the washing liquid to become soluble in the washing liquid. Examples include copper oxide powder with sodium chloride impurities, ferrous hydroxide with sodium sulfate impurities, and copper oxalate with hydrochloric acid, sodium chloride, and ammonium chloride impurities. The washing liquid used in the present invention is at least one of tap water, pure water, and an acid solution. The acid solution is an aqueous solution of an inorganic acid and / or an organic acid, and the specific choice depends on the process standards and the washed substance and its impurities. For impurities such as iron compounds that are easily soluble in acid but poorly soluble in water, or impurities that hydrolyze and precipitate in water, an acid solution is used as the washing liquid. The method of the present invention facilitates the use of the large space within the electrolytic cell outside the filter bag-enclosed electrodes to clean the washed substance. This improves the weight ratio of washing liquid to washed substance during cleaning, allowing soluble impurities to fully dissolve in the washing liquid and be more easily concentrated and removed, thereby reducing purification time and total water consumption. Therefore, compared with the process of Chinese Patent Application No. 202310528764.7, the present invention can reduce the washing time and / or number of times for removing soluble impurities, improve the purification efficiency, and does not increase or even reduces the total amount of water used for washing.

[0019] In step (3), the function of the electrodes is to enrich impurity ions by utilizing electric field force. During operation, an electric field is established in the electrolyte between the electrolytic anode and the electrolytic cathode, so that the impurity anions with negative charge in the washing liquid are electrically attracted by the electrolytic anode and enriched around the electrolytic anode or introduced into the filter bag wrapped around the electrolytic anode. At the same time, the impurity cations with positive charge in the washing liquid are attracted by the electrolytic cathode and enriched around the electrolytic cathode or introduced into the filter bag wrapped around the electrolytic cathode. The solution containing impurity ions is discharged out of the electrolytic cell through the pipette.

[0020] The present invention can be improved as follows: during the ionization and impurity removal operation, part of the washing liquid enriched with impurity ions is sucked away from the electrolytic cell through the liquid pipe, and washing liquid containing less or no impurity ions is added to the electrolytic cell.

[0021] Preferably, a washing liquid containing little or no impurity ions is added to the filter bag, or a washing liquid containing little or no impurity ions is added to the filter bag and the space outside the filter bag in the electrolytic cell. By adding washing liquid to the filter bag, the present invention increases the internal hydraulic pressure of the filter bag, causing solid matter adhered to the outside of the filter bag to be squeezed out by the liquid seeping from the filter bag and fall back into the washing liquid outside the filter bag, preventing clogging of the pores in the filter bag material and ensuring smooth migration of ions and water.

[0022] The present invention can also be improved as follows: when adding washing liquid containing less or no impurity ions to the electrolytic cell or after the adding operation is completed, the vibrator is turned on to shake off the solid matter adhering to the filter bag.

[0023] Preferably, when the washing liquid containing less or no impurity ions is added to the electrolytic cell, the liquid level in the filter bag is made higher than the liquid level outside the filter bag, or the water pressure in the filter bag is increased by using a faster liquid inlet flow rate in the filter bag, so that the liquid in the filter bag seeps out from the inside to the outside, and the solids adhered to the filter bag are squeezed out of the bag by the vibration of the vibrator, thereby accelerating the recovery of the filtering function of the filter holes of the filter bag.

[0024] The present invention can be improved as follows: the vibrator is activated according to time control.

[0025] The present invention can be improved by providing a liquid suction pipe on and / or near at least one electrode outside the filter bag (i.e., the electrode not enclosed by the filter bag) to remove ions accumulated around the electrode. To avoid a large amount of the washed material being sucked away, a slower liquid suction speed or a lower liquid suction frequency is preferably used, and / or liquid suction is performed after the washed material has settled.

[0026] The present invention can be improved as follows: an ion exchange resin pure water device is used to remove impurity ions from the washing liquid extracted during the ionization and impurity removal operation or the washing waste liquid rich in impurity ions obtained after the operation is completed, to obtain a washing liquid containing less or no impurity ions, which is then circulated and added to the electrolytic cell for reuse.

[0027] The present invention can also be improved as follows: before the ionization impurity removal operation, the solid material to be washed is mechanically ground and crushed or ultrasonically impacted to increase the contact area between the soluble impurities and the washing liquid during the ionization impurity removal operation, so that the soluble impurities contained in the material to be washed are more easily dissolved in the washing liquid.

[0028] The present invention can also be improved as follows: when the method of the present invention is used to remove chloride ion impurities in the washed material, the electrolysis current of the electrolysis power supply is increased during the ionization and impurity removal operation, so that the chloride ion impurities enriched near the electrolysis anode are oxidized by the electrolysis anode to become chlorine gas and precipitated and removed.

[0029] The present invention can also be improved as follows: an agitator is used in the space outside the filter bag in the electrolytic cell to stir the solid-liquid mixture of the washed substance and the washing liquid to accelerate the soluble impurities in the washed substance to leave the washed substance and dissolve in the washing liquid. Preferably, the agitator is used to intermittently stir the solid-liquid mixture of the washed substance and the washing liquid, and the electrolysis power supply is turned off each time stirring is performed. After stirring stops, the electrolysis power supply is turned on for ionization and impurity removal only after the solid matter therein has partially or completely settled, so as to reduce the occurrence of unexpected electrochemical side reactions caused by the solid washed substance contacting the electrolysis electrode. More preferably, during stirring, the electrodes and the filter bag are partially or completely lifted off the liquid surface to provide a larger stirring space for the solid-liquid mixture formed by the washed substance and the washing liquid, further promoting the dissolution of soluble impurities into the washing liquid.

[0030] The present invention can also be improved as follows: a hot and cold temperature exchanger is used to heat the washing liquid in the electrolytic cell to accelerate the desorption of impurity ions on the surface of the washed material, making it easier for the impurity ions to be enriched around the corresponding electrodes, thereby improving the washing efficiency.

[0031] The present invention can also be improved by using an electrolysis voltage greater than the electrolyte decomposition voltage to accelerate the ionization and impurity removal process. The electrolyte decomposition voltage is defined as the critical value at which the voltage applied between the electrolysis anode and the electrolysis cathode by the electrolysis power supply under static conditions causes the washing liquid in the electrolytic cell to electrolyze a trace amount of oxidizing gas or a trace amount of reducing gas. The electrolyte decomposition voltage is dependent on various factors, including the electrolyte concentration, viscosity, temperature, distance between the cathode and anode electrodes, and the materials used for the cathode and anode electrodes.

[0032] The present invention can also be improved by detecting the conductivity of the washing liquid to determine whether the impurity concentration in the washing liquid within the electrolytic cell meets the concentration standard set by the process requirements. The conductivity of the washing liquid indirectly reflects the concentration of soluble impurities in the washing liquid. Under the same conditions, the higher the impurity concentration in the washing liquid, the greater the conductivity of the washing liquid.

[0033] The solution adopted by the present invention to achieve the second purpose is:

[0034] A device for removing soluble impurities, characterized in that it comprises: an electrolytic cell, an electrolytic anode, an electrolytic cathode and an electrolytic power supply, wherein:

[0035] An electrolytic anode and an electrolytic cathode are arranged in the electrolytic cell, and the electrolytic anode and the electrolytic cathode are respectively connected to the positive electrode and the negative electrode of the electrolytic power supply; at least one electrolytic anode and / or electrolytic cathode is wrapped by the filter bag;

[0036] A vibrator for vibrating the filter bag and a liquid suction pipe connected to the outside of the electrolytic cell are provided; the liquid suction port of the liquid suction pipe is provided in the filter bag, and each filter bag has at least one liquid suction port.

[0037] The electrolytic cell is made of a polymer resin material and / or a metal coated or wrapped with an anti-corrosion insulating material.

[0038] The electrolysis anode is an insoluble anode, and the surface material thereof in contact with the washing liquid is one or more selected from the group consisting of gold, platinum, titanium-based coating, conductive graphite, titanium, and nickel; the electrolysis cathode is an insoluble cathode, and the surface material thereof in contact with the washing liquid is one or more selected from the group consisting of gold, platinum, titanium, nickel, silver, copper, an alloy containing at least one of the above metals, stainless steel, and conductive graphite.

[0039] The pipette and the electrode are installed and integrated as one body, as shown in FIG1 ; or the electrode and the pipette are each in an independent structure and placed in a filter bag.

[0040] The vibrator can be an electric vibrator and / or a pneumatic vibrator. The vibrator is secured to the filter bag or to a fixed component in contact with the filter bag using a fastening method. The fastening method may include bundling, sewing, welding, or placement in a fixed pocket, so long as the vibrating action of the vibrator is transmitted to the filter bag. The number and mounting location of the vibrators are not limited, as long as they can vibrate the filter bag.

[0041] The present invention can be improved as follows: a solid-liquid separator is added, and the electrolytic cell is connected to the solid-liquid separator via a pipeline and a pump. The solid-liquid separator is selected from a filter press, a filter, and a centrifuge.

[0042] The present invention can also be improved as follows: a temporary storage tank is added for temporarily storing materials and clean water, or for washing and soaking substances; it is connected to at least one container or equipment in the device of the present invention, such as the electrolytic cell, solid-liquid separator, other temporary storage tanks, etc., through a pipeline.

[0043] The present invention can also be improved as follows: an ion exchange resin pure water device is added, and the ion exchange resin pure water device is connected to at least one container or device in the device of the present invention, such as the solid-liquid separator, electrolytic cell, temporary storage tank, etc., by a pipeline.

[0044] The present invention can also be improved as follows: a mechanical grinding mill and / or an ultrasonic generator is added to break up the solid material being cleaned and accelerate the dissolution of soluble impurities for ionization collection and removal. The ultrasonic generator is installed in the electrolytic cell or the temporary storage tank used for breaking up the material being cleaned.

[0045] The present invention can also be improved as follows: a filter bag shaping frame is added to the filter bag to fix the filter bag and maintain the inner cavity space of the filter bag, which is more conducive to enriching impurity ions and absorbing and discharging waste liquid. The filter bag shaping frame is a frame or box frame made of a hard material that is insoluble in the washing liquid. When the filter bag shaping frame adopts a box frame structure, at least one side thereof is provided with through holes and / or electric field line through holes, and the electric field line through holes are arranged on the path through which the electric field lines between the electrolytic anode and the electrolytic cathode immersed in the electrolyte pass during the electrolysis operation. Preferably, the filter bag shaping frame adopts a through-hole resin material box frame as shown in Figure 2, and the filter bag is inserted inside or outside it.

[0046] The present invention can also be improved as follows: a water feeding pipe is added to add a washing liquid containing less or no impurity ions to the space inside the filter bag and / or outside the filter bag in the electrolytic cell.

[0047] The present invention can also be improved as follows: an exhaust pipe is added to the filter bag shaping frame to collect and treat the waste gas escaping from the filter bag.

[0048] The present invention can also be improved as follows: an exhaust gas treatment tank is added to collect and treat the chlorine gas generated by anode electrolysis. The exhaust gas treatment tank is selected from a vacuum jet exhaust gas treatment tank and / or a spray tower exhaust gas treatment tank, and is connected to the electrolytic cell via a gas pipeline.

[0049] The present invention may also be improved by adding sensors and a logic program controller to monitor the operating process and enable the device to automatically control operation according to a pre-programmed program. The sensors are selected from one or more of a thermometer, a liquid level meter, a conductivity meter, a colorimeter, a hydrogen concentration detector, a chlorine concentration detector, a redox potentiometer, and a pH meter. The logic program controller is electrically connected to the signal output end of the sensor and is also electrically connected to at least one of the electrolysis power supply, valve, pump, vibrator, hot and cold temperature exchanger, ultrasonic generator, grinder, and stirrer in the device of the present invention, and controls the device according to the values ​​measured by the sensors and / or the set time.

[0050] The present invention can also be improved as follows: a hydrogen high altitude discharge pipe is added to discharge the small amount of hydrogen produced during the ionization and impurity removal operation safely at high altitude. The hydrogen high altitude discharge pipe is connected to the electrolytic cell by a pipe.

[0051] The present invention can also be improved as follows: a hot and cold temperature exchanger is added to the electrolytic cell and / or temporary storage tank so that the temperature of the washing liquid therein meets the production set temperature range.

[0052] The present invention can also be improved by adding a stirring device to the space outside the filter bag in the electrolytic cell to stir the solid-liquid mixture of the material being washed and the washing liquid, thereby accelerating the enrichment of impurity ions in the washing liquid near the electrodes where they are electrically attracted to each other, thereby improving the purification efficiency. The stirring device can be a liquid flow stirrer and / or an impeller stirrer.

[0053] The present invention can also be improved as follows: the bottom of the electrolytic cell adopts a funnel-shaped structure to increase the bottom solution space outside the filter bag in the electrolytic cell, so as to facilitate the upward backwash washing and stirring of the washed material that settles downward under the action of gravity to help impurity ions separate from the washed material, and facilitate the sedimentation and collection of the washed material after washing.

[0054] The present invention can also be improved as follows: a flow regulating valve is provided on the liquid pipe so as to control the discharge flow of the washing liquid enriched with impurity ions according to the process conditions.

[0055] Compared with the prior art, the present invention has the following beneficial effects:

[0056] The method of the present invention utilizes the combined force of the filter bag and the vibrator to prevent the solid washed matter from having a large area of ​​close contact with the filter bag, and effectively prevents the washed matter from clogging the filter bag and affecting the removal effect of soluble impurities, thereby improving the purification efficiency.

[0057] The method of the present invention utilizes the large internal space outside the filter bag within the electrolytic cell to clean the material being washed, allowing soluble impurities to fully dissolve in the wash solution and be more easily concentrated and removed. This reduces the time and / or frequency of washing, while maintaining or even reducing the total amount of water used for washing, thereby achieving water conservation.

[0058] The method of the present invention can realize recycling and reuse of the produced washing wastewater by adopting ion resin pure water equipment to reduce environmental pollution.

[0059] When the washing liquid is heated in the method of the present invention, the efficiency of ionizing impurities can be further improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0060] FIG1 is a schematic diagram of the structure of the pipette and the electrode installed as one body according to the present invention, wherein B is a right side view of A;

[0061] FIG2 is a schematic diagram of the box frame structure of the present invention;

[0062] FIG3 is a schematic diagram of an apparatus for removing soluble impurities according to Example 1 of the present invention.

[0063] FIG4 is a schematic diagram of an apparatus for removing soluble impurities according to Example 2 of the present invention.

[0064] FIG5 is a schematic diagram of an apparatus for removing soluble impurities according to Example 3 of the present invention.

[0065] Figure 6 is a schematic diagram of an apparatus for removing soluble impurities according to Example 4 of the present invention. Figure 6-1 is a partial enlarged view of Figure 6 , and Figure 6-2 is a partial enlarged view of Figure 6 . Figures 6-1 and 6-2 together constitute Figure 6 .

[0066] FIG7 is a schematic diagram of an apparatus for removing soluble impurities according to Example 5 of the present invention.

[0067] FIG8 is a schematic diagram of the device of Comparative Example 2.

[0068] Reference numerals

[0069] 1-electrolytic cell, 2-electrolytic anode, 3-electrolytic cathode, 4-filter bag, 5-pipette, 6-vibrator, 7-solid-liquid separator, 8-filter bag shaping frame, 9-water adding pipe, 10-electrolytic power supply, 11-ion resin pure water equipment, 12-grinding mill, 13-ultrasonic generator, 14-exhaust pipe, 15-hot and cold temperature exchanger, 16-impeller agitator, 17-liquid flow agitator, 18-temporary storage tank, 19-sensor, 20-logic program controller, 21-flow control valve, 22-Valve, 23-Pump, 24-Substance to be washed, 25-Soluble impurities, 26-Washing liquid with little or no impurity ions, 27-Substance to be washed and purified, 28-Washing liquid, 29-Electrolytic cell cover, 30-Electrode mounting hole, 31-Through hole, 32-Electric field line through hole, 33-Waste gas treatment tank, 34-Vacuum ejector, 35-Spray tower, 36-Chlorine, 37-Hydrogen, 38-High-altitude hydrogen discharge pipe, 39-Washing waste liquid, 40-Solid powder conveying pipe, 41-Alkaline waste gas reaction liquid, 42-Filter bag lifter, 43-Cleaning tank area.

[0070] In the drawings and the following embodiments, "reference numeral-number" is used to indicate one of multiple components of the same type in a device; for example, electrolytic cell 1-1 refers to one of the electrolytic cells, electrolytic cell 2-2 refers to the second electrolytic cell, and vibrators 6-1 to 6-4 refer to the four vibrators 6-1, 6-2, 6-3, and 6-4. "Reference numeral / reference numeral" indicates that a component may be one of different types; for example, "2 / 3" in the drawings means that the component may be either the electrolytic anode 2 or the electrolytic cathode 3. DETAILED DESCRIPTION

[0071] The process technology scheme of the present invention is described in detail below in conjunction with specific embodiments so that those skilled in the art can better understand and implement it.

[0072] In the following examples, the electrolytic cell capacity is 350 L. The electrolytic cell, electrodes, temporary storage tank, agitator, pipette, filter bag, and exhaust gas treatment tank used are all products of Yegao Environmental Protection Equipment Manufacturing Co., Ltd. in Foshan, Guangdong Province. The logic program controller, sensor, solid-liquid separator, and chemical raw materials are all commercially available products. In addition to those listed above, those skilled in the art may also select other products with similar performance to those listed above, and any of these products can achieve the objectives of the present invention.

[0073] As shown in Figure 1, it is a schematic diagram of the structure of the liquid pipette and the electrode installation. At least one liquid pipette 5 is fixedly installed on the surface of the electrolytic anode 2 or the electrolytic cathode 3, and a flow control valve 21 is provided on the upper end of the liquid pipette 5.

[0074] FIG2 is a schematic diagram of a box frame structure specifically used as a filter bag shaping frame.

[0075] The filter bag shaping frame 8 is a box-frame structure made of a polymer material. The top of the frame is equipped with a liquid suction pipe 5, a water supply pipe 9, an exhaust pipe 14, and an electrode mounting hole 30. The bottom of the frame is provided with a through hole 31, and at least one side of the frame is provided with an electric field line through hole 32.

[0076] Example 1

[0077] As shown in FIG1 , the device for removing soluble impurities according to Example 1 of the present invention includes an electrolytic cell 1 , an electrolytic anode 2 , an electrolytic cathode 3 , a filter bag 4 , a pipette 5 , a vibrator 6 , an electrolytic power supply 10 , an impeller stirrer 16 , and a pump.

[0078] The electrolytic cell 1 is provided with an electrolytic anode 2 and an electrolytic cathode 3. The electrolytic anode 2 is connected to the positive electrode of an electrolytic power source 10, and the electrolytic cathode 3 is connected to the negative electrode of the electrolytic power source 10. A liquid pipette 5-1 is positioned adjacent to the electrolytic anode 2. The electrolytic cathode 3 is wrapped in a filter bag 4, with the bottom of the filter bag 4 partially or completely separated from the bottom surface of the electrolytic cell 1. A liquid pipette 5-2 is positioned adjacent to the electrolytic cathode 3, with the liquid suction port of the liquid pipette 5-2 located within the filter bag 4. Vibrators 6-1 and 6-2 are respectively fixedly mounted on the filter bag 4 to vibrate the filter bag 4. An impeller agitator 16 is installed within the electrolytic cell 1.

[0079] The material of the electrolytic anode 2 is gold, and the material of the electrolytic cathode 3 is conductive graphite.

[0080] The vibrator 6 - 1 and the vibrator 6 - 2 are both electric vibrators.

[0081] The liquid pipette 5-1 and the liquid pipette 5-2 are respectively provided with a metering pump 23-1 and a metering pump 23-2.

[0082] In this embodiment, the substance to be washed 24 is basic copper carbonate, and the soluble impurities contained therein are sodium chloride impurities 25, and the impurity concentration is 0.7%; the initially added washing liquid 26 is pure water.

[0083] The method for removing soluble impurities in this embodiment includes the following steps:

[0084] 1. Using the apparatus shown in FIG3 , a washing liquid 26 and a substance to be washed 24 are quantitatively added to the electrolytic cell 1 to form a solid-liquid mixture. The impeller agitator 16 is activated, and during the addition process, the substance to be washed is dispersed and mixed in the washing liquid for 5 minutes, so that soluble impurities dissolve in the washing liquid to form impurity ions. The impeller agitator 16 is then turned off, and the solid-liquid mixture in the electrolytic cell 1 is allowed to stand for 10 minutes to allow the substance to settle to the bottom of the cell.

[0085] 2. Turn on the electrolysis power supply 10 and start working. The chloride ions, one of the impurity ions in the washing liquid 28, are enriched near the electrolytic anode by the electric field force and electrolyze a trace amount of chlorine gas. The sodium ions, another impurity ion, are also affected by the electric field force and migrate into the filter bag, causing hydrogen gas to be electrolyzed at the electrolytic cathode. Start the metering pump 23-2 and use the pipette 5-1 to aspirate and drain the chloride ion solution with a high concentration around the electrolytic anode 2. Start the metering pump 23-3 and use the pipette 5-2 to aspirate and drain the sodium ion solution with a high concentration accumulated in the filter bag. Start the vibrators 6-1 and 6-2 to shake off the solid powder particles adhering to the filter bag.

[0086] 3. During the operation, the washing liquid 26 containing little or no impurity ions is added to the electrolytic cell 1 according to the liquid level; the washing liquid 28 in the electrolytic cell 1 is sampled for inspection. When the impurity ion concentration is reduced to below the process standard value of solution conductivity ≤ 1000μs / cm, the ionization and impurity removal process is completed, and the electrolysis power supply, vibrator and metering pump on the pipette are turned off.

[0087] 4. The solid-liquid mixture in the electrolytic cell 1 is extracted and separated into solid and liquid using a solid-liquid separator. The resulting filter residue is the washed material 27 after washing and purification, and the filtrate is the washing waste liquid 39.

[0088] The process data before and after the ionization impurity removal operation are listed in Table 1. The washing liquid used in the entire operation was 7.5 times the weight of the material being washed, and the entire operation took 7 hours.

[0089] Example 2

[0090] As shown in FIG4 , the device for removing soluble impurities according to Example 2 of the present invention includes an electrolytic cell 1, an electrolytic anode 2, an electrolytic cathode 3, two filter bags 4-1 and 4-2, two liquid suction pipes 5-1 and 5-2, four vibrators 6-1 to 6-4, a solid-liquid separator 7, two filter bag shaping frames 8-1 and 8-2, two exhaust pipes 14, a hot and cold temperature exchanger 15, a liquid flow agitator 17, a temporary storage tank 18, a sensor 19, two flow control valves 21-1 and 21-2, an electrolytic cell cover 29, a hydrogen high-altitude safety discharge pipe 38, valves, and a pump.

[0091] The electrolytic cell 1 is provided with an electrolytic anode 2 and an electrolytic cathode 3. The electrolytic anode 2 is connected to the positive electrode of an electrolytic power source 10, and the electrolytic cathode 3 is connected to the negative electrode of the electrolytic power source 10. A cell cover 29 is provided on the top of the electrolytic cell 1. The bottom of the electrolytic cell 1 is a funnel-shaped structure, with a three-way pipe at the bottom of the funnel. One of the pipes is a liquid agitator 17, and the other is connected to the solid-liquid separator 7 via a pipe equipped with a valve 22-2 and a pump 23-1. The liquid agitator 17 is located above the bottom of the electrolytic cell 1. The liquid outlet is connected to the three-way pipe at the bottom of the funnel of the electrolytic cell 1 via a pipe equipped with a pump 23-4 and a valve 22-1. This facilitates backwashing and mixing of the washed material 24, thereby improving washing efficiency. The filter bag shaping frames 8-1 and 8-2 are frame structures, which respectively fix the filter bags 4-1 and 4-2 on their exteriors, and the bottoms of the two filter bags are completely away from the bottom surface of the electrolytic cell 1; the filter bag 4-1 is wrapped with a liquid suction pipe 5-1 and an electrolytic anode 2, and the filter bag 4-2 is wrapped with a liquid suction pipe 5-2 and an electrolytic cathode 3. The above-mentioned liquid suction pipes and electrodes adopt the integrated structure shown in Figure 1, and the liquid suction ports of the liquid suction pipes are in the corresponding filter bags and next to the corresponding electrolytic electrodes; the liquid suction pipe 5-1 is connected to the temporary storage tank 18 through a pipeline provided with a valve 21-1 and a pump 23-2, and the liquid suction pipe 5-2 is connected to the temporary storage tank 18 through a pipeline provided with a valve 21-2 and a pump 23-3.

[0092] The material of the electrolytic anode 2 is nickel, and the material of the electrolytic cathode is stainless steel.

[0093] The four vibrators 6-1 to 6-4 are pneumatic vibrators. Vibrators 6-1 and 6-2 are fixed on the filter bag 4-1, and vibrators 6-3 and 6-4 are fixed on the filter bag 4-2.

[0094] The solid-liquid separator 7 is a common filter, which is also connected to the temporary storage tank 18 through a pipeline.

[0095] The hot and cold temperature exchanger 15 is installed on the electrolytic cell 1 and is used to control the temperature of the washing liquid 28 according to the set value of the sensor 19; the sensor 19 is a thermometer, and its probe is immersed in the washing liquid of the electrolytic cell 1 during operation.

[0096] The filter bag shaping frames 8 - 1 and 8 - 2 are provided with exhaust pipes 14 - 1 and 14 - 2 respectively, and the exhaust pipe 14 - 2 is connected to a hydrogen high-altitude safety discharge pipe 38 .

[0097] In this embodiment, the substance to be washed 24 is ferrous hydroxide, and the soluble impurity contained therein is sodium sulfate; the washing liquid 26 initially added is tap water.

[0098] The electrolytic cell cover 29 is used to prevent external air from oxidizing the ferrous hydroxide in the electrolytic cell.

[0099] The method for removing soluble impurities in this embodiment includes the following steps:

[0100] 1. Using the apparatus shown in FIG4 , a washing liquid 26 and a substance to be washed 24 are added to the electrolytic cell 1 to form a solid-liquid mixture, and soluble impurities dissolve in the washing liquid to form impurity ions;

[0101] 2. Turn on the electrolysis power supply, start each vibrator, adjust the valves connected to the liquid pipettes for flow control, and start pumps 23-2 and 23-3 to perform the liquid suction operation. During the operation, new washing liquid 26 is added to the electrolytic cell 1 in a controlled manner. The liquid flow agitator 17 continuously backwashes the washed material accumulated at the bottom of the funnel-shaped cell upward, and the vibrators shake off the washed material adhering to the filter bags. The impurity ions sulfate and sodium ions are respectively enriched in the filter bag containing the electrolytic anode and the filter bag containing the electrolytic cathode, and are respectively pumped into the temporary storage tank 18 through the liquid pipettes installed in the filter bags. During the operation, the temperature of the washing liquid 28 is controlled by sensor 19, which is a thermometer, to maintain 50°C to accelerate the dissolution of soluble impurities in the washing liquid.

[0102] 3. The washing liquid 28 in the electrolytic cell 1 is sampled for inspection. When the impurity ion concentration is lower than the set process standard of 0.3 g / L, the ionization and impurity removal process is completed, and the electrolysis power supply, vibrator, pumps 23-2 and 23-3, and liquid flow agitator 17 are shut down.

[0103] 4. Open valve 22-2 and start pump 23-1 to separate the solid-liquid mixture in electrolytic cell 1 through solid-liquid separator 7. The resulting filter residue is the washed substance 27 (ferrous hydroxide) after washing and purification, and the filtrate is the washing waste liquid 39. The filter residue is retained in the filter, and the filtrate is drained into temporary storage tank 18.

[0104] The process data before and after the ionization impurity removal operation are listed in Table 1. The washing liquid used in the entire operation was 7 times the weight of the material being washed, and the entire operation took 6.5 hours.

[0105] A higher temperature in the electrolytic cell further accelerates the desorption of impurity ions from the surface of the material being cleaned, allowing them to more easily accumulate around the corresponding electrodes, thereby improving cleaning efficiency. During the operation, when sensor 19, i.e., a thermometer, controls the temperature of the cleaning liquid 28 at 70°C, the entire process takes six hours.

[0106] Example 3

[0107] As shown in FIG5 , the device for removing soluble impurities according to Example 3 of the present invention includes an electrolytic cell 1, an electrolytic anode 2, an electrolytic cathode 3, two filter bags 4-1 and 4-2, two liquid suction pipes 5-1 and 5-2, four vibrators 6-1 to 6-4, a solid-liquid separator 7, two filter bag shaping frames 8-1 and 8-2, two water supply pipes 9-1 and 9-2, an ion resin pure water device 11, a grinding mill 12, a liquid flow agitator 17, three temporary storage tanks 18-1 to 18-3, valves, and a pump.

[0108] The electrolytic cell 1 is provided with an electrolytic anode 2 and an electrolytic cathode 3. The electrolytic anode 2 is connected to the positive electrode of the electrolytic power supply 10, and the electrolytic cathode 3 is connected to the negative electrode of the electrolytic power supply 10. The discharge port of the electrolytic cell 1 is provided with a liquid flow agitator 17, specifically a liquid flow circulation pipeline equipped with a valve and a pump connected to the feed port of the electrolytic cell 1. The discharge port of the electrolytic cell 1 is also connected to the solid-liquid separator 7 through a pipeline equipped with a valve 22-4 and a pump 23-1. The filter bags 4-1 and 4-2 are respectively embedded in the filter bag shaping frames 8-1 and 8-2. The filter bag shaping frames 8-1 and 8- 2 uses the box-frame structure shown in Figure 2, with the bottoms of the two filter bags completely clear of the bottom surface of the electrolytic cell 1. Filter bag 4-1 contains a water supply pipe 9-1, a liquid suction pipe 5-1, and an electrolytic anode 2, while filter bag 4-2 contains a water supply pipe 9-2, a liquid suction pipe 5-2, and an electrolytic cathode 3. These liquid suction pipes and electrodes adopt the integrated structure shown in Figure 1, with the liquid suction ports of the liquid suction pipes located in the corresponding filter bags, next to the corresponding electrolytic electrodes. The liquid suction pipes 5-1 and 5-2, respectively, pass through valves 21-1 and 21-2, and are then connected to the temporary storage tank 18-2 via a pump 23-2. The liquid outlet of the temporary storage tank 18-3 is connected to the water supply pipe 9-1 and the water supply pipe 9-2, respectively, via pipes equipped with valve 22-5 and pump 23-5. Furthermore, the outlet is connected to the area of ​​the electrolytic cell 1 outside the filter bags via a pipe equipped with valve 22-3.

[0109] The material of the electrolysis anode is titanium, and the material of the electrolysis cathode is titanium.

[0110] The four vibrators 6-1 to 6-4 are pneumatic vibrators. The vibrators 6-1 and 6-2 are fixedly mounted on the filter bag 4-1, and the vibrators 6-3 and 6-4 are fixedly mounted on the filter bag 4-2.

[0111] The solid-liquid separator 7 is a filter press, which is also connected to the temporary storage tank 18-2 through a pipeline.

[0112] The grinding mill 12 is connected to the electrolytic cell 1 through a solid powder conveying pipe 40 .

[0113] The sensor 19 is a conductivity meter, which is arranged in the electrolytic cell 1 and is used to measure the conductivity value in the washing liquid 28 to determine the concentration of soluble impurities in the washing liquid.

[0114] The ion resin water purification equipment is used to treat the washing wastewater 39 and produce a washing liquid 26 with little or no impurity ions to be fed back into the electrolytic cell. The ion resin water purification equipment 11 is connected to the temporary storage tank 18-2 and the temporary storage tank 18-3 through pipelines equipped with pumps.

[0115] The temporary storage tank 18-1 is used to store the washed material 27 after washing and purification obtained by solid-liquid separation. The temporary storage tank 18-2 is used to temporarily store the washing waste liquid 39. The temporary storage tank 18-3 is used to temporarily store the washing liquid 26 with little or no impurity ions obtained by the washing waste liquid 39 being purified by the ion resin pure water equipment 11.

[0116] In this embodiment, the substance to be washed 24 is copper oxalate, and the soluble impurities contained therein are ammonium oxalate and sodium chloride. The washing liquid 26 initially added is industrial pure water.

[0117] This embodiment provides a method for removing soluble impurities, comprising the following steps:

[0118] 1. Lumpy material to be cleaned 24-1 is placed in a grinding mill for pulverization. The processed powdered material to be cleaned 24-2 is quantitatively added to the space outside the filter bag in the electrolytic cell 1. A cleaning liquid 26 containing little or no impurity ions is added to the space outside the filter bag in the electrolytic cell 1. The cleaning liquid and the material to be cleaned are mixed in the electrolytic cell 1 to form a solid-liquid mixture. Soluble impurities dissolve in the cleaning liquid to form impurity ions. The cleaning liquid is then applied to the filter bags 4-1 and 4-2.

[0119] 2. Turn on the electrolysis power supply 10 and start the liquid flow agitator 17 to enrich the impurity ions. During the operation, the pipette is repeatedly used to extract the washing liquid enriched with impurity ions and the water pipe is used to replenish the washing liquid with less or no impurity ions according to the process design interval.

[0120] Specifically, pump 23-2 is activated or deactivated according to a set time schedule to intermittently pump the solution from the two filter bags through suction pipes 5-1 and 5-2, respectively, draining the waste washing liquid 39 into the temporary storage tank 18-2. Each vibrator is activated intermittently according to time control. According to the process design, each time pump 23-2 is deactivated, pump 23-5 is activated to add washing liquid 26 containing little or no impurity ions to filter bags 4-1 and 4-2 through water pipes 9-1 and 9-2, respectively, at a faster inflow rate. This increases the pressure inside the bags to a higher level than outside the bags. Simultaneously, the vibrators on the filter bags are activated, forcing the solution inside the bags out of the bags and squeezing any solids adhering to the bags out of the bags, thereby reducing clogging of the filter bag pores.

[0121] 3. When the conductivity value of the washing liquid 28 in the electrolytic cell 1 measured by the sensor 19 reaches the process set value of 800μs / cm, the ionization and impurity removal process is completed, and the electrolysis power supply, the pump connected to the pipette or water pipe, and the liquid flow agitator are turned off;

[0122] 4. Open valve 22 and start pump 23-2 to separate the solid-liquid mixture in electrolytic cell 1 through solid-liquid separator 7. The resulting residue is the washed and purified material 27, i.e., copper oxalate. The filtrate is the washing waste liquid 39. The residue is temporarily placed in tank 18-1, and the filtrate is drained to tank 18-2 for temporary storage.

[0123] 5. The washing waste liquid 39 is sent to the ion resin pure water equipment for treatment. The washing liquid with little or no impurity ions obtained after treatment is temporarily stored in the tank 18-3 and returned to the electrolytic tank 1 for use according to the process requirements.

[0124] The process data before and after the above ionization impurity removal operation are listed in Table 1.

[0125] Example 4

[0126] As shown in FIG6 , an apparatus for removing soluble impurities according to Example 4 of the present invention is shown, which includes two electrolytic cells 1-1 and 1-2, two electrolytic anodes 2-1 and 2-2, two electrolytic cathodes 3-1 and 3-2, four filter bags 4-1 to 4-4, four liquid pipettes 5-1 to 5-4, ten vibrators 6-1 to 6-10, three solid-liquid separators 7-1 to 7-3, four filter bag shaping frames 8-1 to 8-4, four water supply pipes 9-1 to 9-4, two electrolytic power supplies 10-1 and 10-2, an ion resin pure water device 11, a grinding mill 12, three ultrasonic generators 13-1 to 13-3, two liquid flow agitators 17-1 and 17-2, five temporary storage tanks 18-1 to 18-5, thirteen sensors 19-1 to 19-13, a logic program controller 20, an exhaust gas treatment tank 33, and a plurality of valves and pumps.

[0127] The electrolytic cell 1-1 and the electrolytic cell 1-2 are used for performing two-stage ionization and impurity removal on the washed substances.

[0128] The electrolytic cell 1-1 is provided with an electrolytic anode 2-1 and an electrolytic cathode 3-1. The electrolytic anode 2-1 is connected to the positive electrode of the electrolytic power supply 10-1, and the electrolytic cathode 3-1 is connected to the negative electrode of the electrolytic power supply 10-1. The electrolytic cell 1-1 is provided with a liquid flow agitator 17-1, specifically a liquid flow circulation pipeline provided with a valve and a pump. The filter bags 4-1 and 4-2 are respectively embedded with filter bag shaping frames 8-1 and 8-2, so that the bottoms of the two filter bags are completely away from the bottom surface of the electrolytic cell 1. The filter bag shaping frames 8-1 and 8-2 adopt a box frame structure. The filter bag 4-1 is wrapped with a water supply pipe 9-1, a liquid suction pipe 5-1, an electrolytic power supply 10-1, and a liquid circulation pipe 17-1. The electrolysis anode 2-1 is equipped with sensors 19-1 and 19-2. The filter bag 4-2 is wrapped with a water supply pipe 9-2, a liquid pipette 5-2, and an electrolysis cathode 3-1 and equipped with sensors 19-4 and 19-5. The above-mentioned liquid pipette and electrode adopt the integrated structure shown in Figure 1. The liquid suction port of the liquid pipette is in the corresponding filter bag and next to the corresponding electrolysis electrode; the filter bag 4-1 is also equipped with three vibrators 6-1, 6-2 and 6-9, and the filter bag 4-2 is also equipped with three vibrators 6-3, 6-4 and 6-10. Sensors 19-3 and 19-6 are set in the area outside the filter bag in the electrolytic cell 1-1;

[0129] The electrolytic cell 1-2 is provided with an electrolytic anode 2-2 and an electrolytic cathode 3-2. The electrolytic anode 2-2 is connected to the positive electrode of the electrolytic power supply 10-2, and the electrolytic cathode 3-2 is connected to the negative electrode of the electrolytic power supply 10-2. The electrolytic cell 1-2 is provided with a liquid flow agitator 17-2, specifically a liquid flow circulation pipeline equipped with valves and pumps. The filter bags 4-3 and 4-4 are respectively embedded with filter bag shaping frames 8-3 and 8-4, so that the bottoms of the two filter bags are completely away from the bottom surface of the electrolytic cell 1. The filter bag shaping frames 8-3 and 8-4 adopt a box frame structure. The filter bag 4-2 is wrapped with a water supply pipe 9-3, a liquid suction pipe 5-3, an electrolytic anode 2-2 and a sensor. 19-7 and 19-8, the filter bag 4-4 ​​is wrapped with a water supply pipe 9-4, a liquid suction pipe 5-4, an electrolytic cathode 3-2 and is equipped with sensors 19-10 and 19-11. The above-mentioned liquid suction pipe and electrode adopt the integrated structure shown in Figure 1, and the liquid suction port of the liquid suction pipe is in the corresponding filter bag and next to the corresponding electrolytic electrode; the filter bag 4-3 is also equipped with two vibrators 6-5 and 6-6, and the filter bag 4-2 is also equipped with two vibrators 6-7 and 6-8. Sensors 19-9 and 19-12 are installed in the area outside the filter bag in the electrolytic cell 1-2; two ultrasonic generators 13-2 and 13-3 are installed on the bottom outside the electrolytic cell 1-2;

[0130] The discharge port of the electrolytic cell 1-1 is connected to the solid-liquid separator 7-1 via a pipeline provided with a valve 22-1 and a pump 23-1; the discharge port of the electrolytic cell 1-2 is connected to the solid-liquid separator 7-2 via a pipeline provided with a valve 22-4 and a pump 23-3;

[0131] The liquid pipes 5-1 to 5-4 pass through flow control valves 21-1, 21-2, 21-3, and 21-4 respectively and are then connected to the temporary storage tank 18-4 through a pump 23-5.

[0132] The liquid outlet of the temporary storage tank 18-5 is connected to the water supply pipes 9-1 to 9-4 respectively through pipelines equipped with valves 22-6 and pumps 23-7, and is also connected to the area outside the filter bag in the electrolytic cell 1-1 through a pipeline equipped with valve 22-7, connected to the temporary storage tank 18-2 through a pipeline equipped with valve 22-8, and connected to the area outside the filter bag in the electrolytic cell 1-2 through a pipeline.

[0133] The electrolytic anode 2-1 is a titanium-based coated electrode, the electrolytic anode 2-2 is a titanium-based platinum-plated material, the electrolytic cathode 3-1 is a copper plate, and the electrolytic cathode 3-2 is made of nickel.

[0134] The vibrators 6-1 to 6-10 are all pneumatic vibrators.

[0135] The solid-liquid separator 7-1 is a filter press, the solid-liquid separator 7-2 is a centrifuge, and the solid-liquid separator 7-3 is a filter. The solid-liquid separators 7-1 and 7-2 are each connected to a temporary storage tank 18-4 by pipes, while the solid-liquid separator 7-3 is connected to the temporary storage tank 18-4 and the ion resin pure water equipment 11 by pipes.

[0136] The grinding mill 12 is connected to the electrolytic cell 1 via a solid powder conveying pipe 40 and is used to crush the material to be washed 24. The ultrasonic generators 13-2 and 13-3 are used to further crush and clean the material to be washed 24.

[0137] The ion resin water purification equipment 11 is used to treat the washing waste liquid 39 and produce a washing liquid with little or no impurity ions for recycling. The liquid outlet of the ion resin water purification equipment 11 is connected to the temporary storage tank 18-5 by a pipeline.

[0138] The temporary storage tank 18-2 is provided with an ultrasonic generator 13-1 for stirring and mixing the washed material 24-3 with water. The ultrasonic generator 13-1 is connected to the space outside the filter bag in the electrolytic tank 1-2 through a pipeline provided with a valve 22-3 and a pump 23-2.

[0139] The waste gas treatment tank 33 is used to treat the chlorine gas escaping from the anode of the electrolytic cell 1-1, and is connected to the filter bag forming frame 8-1 of the electrolytic cell 1-1 through a pipeline.

[0140] Sensors 19-1, 19-3, 19-5, 19-7, 19-9, 19-11, and 19-13 are all conductivity meters, and sensors 19-2, 19-4, 19-6, 19-8, 19-10, and 19-12 are all liquid level gauges. The programmable logic controller 20 is electrically connected to each of the sensors, the electrolysis power supply, the valves and / or pumps controlling the liquid pipe, the valves and / or pumps controlling the water supply pipe, the vibrator, and other pumps. During operation, the on-site detection data from each sensor is transmitted to the programmable logic controller 20 for processing, ensuring safe production operation according to pre-programmed procedures.

[0141] In this embodiment, the washed substance 24 is copper oxide, and the soluble impurity contained therein is sodium chloride. The initial added washing liquid 26 is industrial pure water, which is mainly used to remove chloride ions, so that the chloride ion content of the copper oxide product reaches the high standard requirement of ≤30mg / kg.

[0142] The method for removing soluble impurities in this embodiment includes the following steps:

[0143] 1. Using the device shown in FIG6 , turn on the power of the device to put the programmable logic controller 20 (PLC) into operation, process the data transmitted by the various sensors on site, and output instructions to make the device run according to the pre-programmed program;

[0144] 2. The crude granular copper oxide product 24-1 is fed into a grinding mill 12 for pulverization to obtain copper oxide powder, which is then fed into the electrolytic cell 1-1 together with the washing liquid 26 to form a solid-liquid mixture. Soluble impurities dissolve in the washing liquid to form impurity ions, and the filter bags 4-1 and 4-2 are respectively soaked in the washing liquid.

[0145] 3. Turn on the electrolysis power supply 10-1 and start the liquid flow agitator 17-1 to enrich the impurity ions. During the operation, the logic program controller 20 repeatedly uses the pipette to pump out the washing liquid enriched with impurity ions and the water pipe to replenish the washing liquid with little or no impurity ions according to the time and process design intervals.

[0146] Specifically, the flow control valves 21-1 and 21-2 corresponding to the liquid pipes 5-1 and 5-2 respectively execute the instructions issued by the logic program controller 20. According to the program, the pump 23-5 is controlled based on the two liquid level gauges of sensors 19-2 and 19-4 to pump out the solution in the filter bags 4-1 and 4-2. The three vibrators on the filter bags 4-1 and 4-2 are activated according to the instructions issued by the logic program controller 20. When the two liquid level gauges of sensors 19-2 and 19-4 reach the low point, the logic program controller 20 is activated. Logic program controller 20 issues a command to shut down pump 23-5 and activate pump 23-7 to inject cleaning solution 26 containing little or no impurity ions into filter bags 4-1 and 4-2 through water supply pipes 9-1 and 9-2, respectively. This causes the liquid level in filter bags 4-1 and 4-2 to rise above the liquid level outside the filter bags of electrolytic cell 1-1. This forces the solution in filter bags 4-1 and 4-2 to seep out and squeezes solid matter adhering to the filter bags away from them, reducing clogging of the filter bag pores. Logic program controller 20 then shuts down pump 23-7 based on the timer and restarts pump 23-5.

[0147] 4. When the values ​​measured by the three conductivity meters 19-1, 19-3, and 19-5 in electrolytic cell 1-1 are all less than or equal to the process set value of 20 μs / cm, the ionization and impurity removal process in electrolytic cell 1-1 is completed. Electrolytic cell 1-1 is shut down, valve 22-1 is opened, and pump 23-1 is started to separate the solid-liquid mixture in electrolytic cell 1-1 through filter press 7-1. The resulting filter residue is the washed material 24-3, and the filtrate is the washing waste liquid 39, which is drained into temporary storage tank 18-4.

[0148] 5. The material to be cleaned 24-3 is placed in a temporary storage tank 18-2 equipped with an ultrasonic generator, where it is mixed and resonated with a washing liquid 26 containing little or no impurity ions. This further breaks down the copper oxide particles into the material to be cleaned 24-4, which is then mixed with the washing liquid 26 to form a solid-liquid mixture. Soluble impurities dissolve in the washing liquid to form impurity ions. A second ionization and impurity removal process is then carried out. The operating procedure is the same as the ionization and impurity removal process in the electrolytic cell 1-1, and the ultrasonic generators 13-2 and 13-3 operate according to the instructions of the logic program controller 20.

[0149] 6. When the values ​​of the three conductivity meters, sensors 19-7, 19-9, and 19-11, reach the process set value of 10 μs / cm, the ionization and impurity removal process in electrolytic cell 1-2 is completed; the operation of electrolytic cell 1-2 is shut down, valve 22-4 is opened, and pump 23-3 is started to perform solid-liquid separation on the solid-liquid mixture in electrolytic cell 1-2. The filter residue obtained is the washed and purified material 27, i.e., copper oxide powder, and the filtrate is the washing waste liquid 39.

[0150] 7. The washing waste liquid 39 in the temporary storage tank 18-4 is treated by the ion resin pure water equipment 11. After the conductivity is tested by the sensor 19-13 therein and it is qualified, the washing liquid with little or no impurity ions is temporarily stored in the temporary storage tank 18-3 and recycled according to the procedure.

[0151] The process data before and after the above ionization impurity removal process are listed in Table 1.

[0152] Example 5

[0153] As shown in FIG7 , the device for removing soluble impurities according to Example 5 of the present invention includes an electrolytic cell 1, an electrolytic anode 2, an electrolytic cathode 3, two filter bags 4-1 and 4-2, two liquid suction pipes 5-1 and 5-2, two vibrators 6-1 and 6-2, two filter bag shaping frames 8-1 and 8-2, two pumps 23-1 and 23-2, and a filter bag lifter 42.

[0154] The electrolytic cell 1 is provided with an electrolytic anode 2 and an electrolytic cathode 3. The electrolytic anode 2 is connected to the positive electrode of the electrolytic power supply 10, and the electrolytic cathode 3 is connected to the negative electrode of the electrolytic power supply 10. The filter bag shaping frames 8-1 and 8-2 are frame structures, and the filter bags 4-1 and 4-2 are fixed therein respectively, so that the bottoms of the two filter bags are completely away from the bottom surface of the electrolytic cell 1. The filter bag 4-1 is wrapped with a pipette 5-1 and an electrolytic anode 2, and the filter bag 4-2 is installed with a pipette 5-2 and an electrolytic cathode 3. The liquid suction port of the pipette is in the corresponding filter bag and next to the corresponding electrolytic electrode; the pipette 5-1 and the pipette 5-2 are respectively provided with a metering pump 23-2 and a metering pump 23-3.

[0155] The material of the electrolysis anode is a titanium-based coating electrode, and the material of the electrolysis cathode is titanium.

[0156] The two vibrators 6-1 and 6-2 are pneumatic vibrators, which are fixedly installed on the filter bag 4-1 and the filter bag 4-2 respectively.

[0157] In this embodiment, the substance to be washed 24 is copper oxalate, and the soluble impurities 25 contained therein are sodium chloride and iron compounds, with an impurity concentration of 1%. The washing liquid 26 used is an acid solution, specifically an aqueous solution of hydrochloric acid and sulfuric acid. The acidity of the acid solution causes the iron in the impure iron compounds to exist in the washing liquid as ions.

[0158] This embodiment provides a method for removing soluble impurities, comprising the following steps:

[0159] 1. Using the apparatus shown in FIG7 , a washing liquid and the material to be washed are added to the electrolytic cell 1 to form a solid-liquid mixture, and soluble impurities dissolve in the washing liquid to form impurity ions;

[0160] 2. Turn on the electrolysis power supply 10 to operate, so that the chloride ions among the impurity ions in the washing liquid 28 are caused to migrate into the filter bag 4-1 by the electric field force, and the sodium ions and iron ions among the impurity ions are caused to migrate into the filter bag 4-2 by the electric field force; start the metering pump 23-1 and use the pipette 5-1 to suck out the solution containing a relatively high concentration of chloride ions in the filter bag 4-1; start the metering pump 23-2 and use the pipette 5-2 to suck out the solution containing a relatively high concentration of sodium ions and iron ions in the filter bag 4-1; start the vibrators 6-1 and 6-2 to shake off the solid powder particles adhering to the filter bag by the washing material;

[0161] 3. During the operation, the filter bag lifter 42 is intermittently started to lift the filter bags 4-1 and 4-2 and stir the solid-liquid mixture in the electrolytic cell 1. The washing liquid 26 containing little or no impurity ions is added to the electrolytic cell 1 according to the liquid level.

[0162] 4. Take a sample of the washing liquid 28 in the electrolytic cell 1 for inspection. When the impurity ion concentration is reduced to below the process standard value of solution conductivity ≤ 1200 μs / cm, the ionization and impurity removal process is completed, and the electrolysis power supply, vibrator and metering pump on the pipette are turned off.

[0163] 5. The solid-liquid mixture in the electrolytic cell 1 is extracted for solid-liquid separation, and the filter residue obtained is the washed material 27 after washing and purification, and the filtrate washing waste liquid 39.

[0164] The process data before and after the above ionization impurity removal operation are listed in Table 1.

[0165] Comparative Example 1

[0166] The material to be washed in this comparative example is the same as that in Example 2, namely ferrous hydroxide containing sodium sulfate as an impurity.

[0167] Clean water is used as the washing liquid to rinse the above chemicals to remove soluble impurities. After each rinse, the impure wash water is removed using a solid-liquid separation device. The water is then replaced and the rinsing process is repeated until the washed material and the washing liquid are thoroughly mixed and stirred, and the resulting solution has an impurity ion concentration below the set process standard of 0.3 g / L.

[0168] In this comparative example, the amount of washing liquid used in each rinsing cycle was 4 times the weight of the material being washed. Rinsing was repeated 5 times, for a total of 20 times. The entire operation of this comparative example took 8 hours.

[0169] Comparative Example 2

[0170] This comparative example employs a method for separating electrolyte impurities from water-insoluble compounds, proposed by the applicant in Chinese patent application No. 202310528764.7, to clean the material being washed. The material being washed in this comparative example is the same as in Example 2, namely, ferrous hydroxide containing sodium sulfate as an impurity.

[0171] As shown in FIG8 , this comparative example employs an electrolytic cell 1 having an electrolytic anode 2 and an electrolytic cathode 3 connected to the positive and negative electrodes of an electrolytic power source 10, respectively. A cleaning tank area 43 is enclosed by a separator between the electrolytic anode 2 and the electrolytic cathode 3, through which the electric field lines pass when power is applied. The separator is a filter bag capable of holding the material to be washed. The area within the electrolytic cell 1 where the electrolytic anode is located is directly connected to the area where the electrolytic cathode is located, forming a shared tank area between the two electrodes. The electrolytic anode 2 is made of platinum, and the electrolytic cathode 3 is made of stainless steel.

[0172] The specific steps for separating sodium sulfate electrolyte impurities from water-insoluble ferrous hydroxide are as follows:

[0173] 1. Place the filter bag containing the material to be washed between the electrolytic anode and the electrolytic cathode in the electrolytic cell to form a cleaning tank area;

[0174] 2. Add clean water to the filter bag as a washing liquid. The washing liquid seeps from the filter bag into the common tank area of ​​the two poles of the electrolytic cell, so that the electrolytic anode and the electrolytic cathode as well as the washed material are immersed in the washing liquid.

[0175] 3. Turn on the electrolysis power supply to carry out electrolysis operation. The impurity ions are pulled out into the washing liquid outside the filter bag by the electric field force, and approach the electrolysis cathode and electrolysis anode respectively, so as to reduce the soluble impurities in the filter bag.

[0176] 4. Until the impurity ion concentration in the washing liquid is lower than the set process standard of 0.3 g / L, the ionization and impurity removal process is completed and the filter bag containing the washed material is taken out of the electrolytic cell to collect the washed and purified material.

[0177] The cleaning liquid used in this comparative example was eight times the weight of the material being cleaned. Furthermore, the rate at which the impurity level in the electrolytic cell decreased during the final stages of the ionization and impurity removal process was significantly slower than in Example 2. After the ionization and impurity removal process, the filter bags were found to be clogged with the material being cleaned. The entire process of this comparative example took 10 hours.

[0178] Table 1 Comparison of process data before and after ionization impurity removal

[0179] The amount of impurities in the washing liquid can be confirmed by using any one or more of the following methods: colorimetry, conductivity detection, and conventional chemical detection methods.

[0180] In addition, after the washing and impurity removal process in Example 4 was completed, the chloride ion content of the washed and purified copper oxide product, i.e., the copper oxide product, was measured using conventional chemical testing methods. The result was 24 mg / L, meeting product requirements. This demonstrates that the completion of cleaning and impurity removal can be indirectly determined by measuring the conductivity of the washing liquid.

[0181] A comparison of Example 2, Comparative Examples 1, and 2 shows that the method of the present invention requires the least amount of washing liquid for washing the same amount of material. Even if the washing wastewater can be deionized and recycled through an ion resin water purification device, the reduced amount of washing liquid used in the present invention can significantly save the time required for solid-liquid separation and deionization, significantly improving washing efficiency.

Claims

1. A method for removing soluble impurities, characterized in that: The following steps are involved: (1) establishing an electrolytic cell, wherein at least one electrode in the electrolytic cell is wrapped by a filter bag, the bottom of the filter bag is at least partially away from the bottom surface of the electrolytic cell, and the electrode is an electrolytic anode and / or an electrolytic cathode; In the electrolytic cell, the electrolytic anode is connected to the positive electrode of the electrolytic power supply, and the electrolytic cathode is connected to the negative electrode of the electrolytic power supply; A vibrator capable of vibrating the filter bag and a liquid suction pipe connected to the outside of the electrolytic cell are provided, wherein the liquid suction port of the liquid suction pipe is provided in the filter bag and each filter bag has at least one liquid suction port; (2) The area outside the filter bag in the electrolytic cell is filled with a washing liquid and a solid material to be washed with soluble impurities to form a solid-liquid mixture, so that the soluble impurities are dissolved in the washing liquid to form impurity ions, and the electrolytic anode and the electrolytic cathode are immersed in the washing liquid; (3) turning on the electrolysis power supply to ionize the impurity ions, and removing the impurity ions accumulated near the electrode by extracting the solution through the pipette and / or converting them into gas through electrolysis; The vibrator is started continuously or intermittently to shake off the washed materials adhering to the filter bag; (4) When the impurity ion concentration in the washing liquid in the electrolytic cell reaches or is lower than the concentration standard set by the process requirements, the impurity removal process of the washed material is completed, and then the solid matter in the electrolytic cell is removed by solid-liquid separation to obtain a washed and purified product.

2. The method for removing soluble impurities according to claim 1, characterized in that: The material of the filter bag is insoluble in the solid-liquid mixture composed of the washed substance and the washing liquid, and the material on at least one side thereof can effectively prevent the solid washed substance from entering the filter bag but can allow water and ions to pass through; The washed substance is a solid substance that is insoluble or slightly soluble in the washing liquid and contains impurities that are soluble in the washing liquid; The washing liquid used is at least one of tap water, pure water and acid solution.

3. The method for removing soluble impurities according to claim 2, characterized in that: The material of the filter bag is at least one of filter cloth, filter plate and filter screen.

4. The method for removing soluble impurities according to claim 3, characterized in that: During the ionization and impurity removal operation, a portion of the washing liquid enriched with impurity ions is sucked away from the electrolytic cell through the liquid suction pipe, and the electrolytic cell is supplemented with washing liquid containing less or no impurity ions.

5. The method for removing soluble impurities according to claim 4, characterized in that: The washing liquid containing less or no impurity ions is added to the filter bag, or the washing liquid containing less or no impurity ions is added to the filter bag and the space outside the filter bag in the electrolytic cell respectively.

6. The method for removing soluble impurities according to claim 5, characterized in that: When the washing liquid containing less or no impurity ions is added to the electrolytic cell or after the adding operation is completed, the vibrator is turned on to shake off the solid matter adhering to the filter bag.

7. The method for removing soluble impurities according to claim 6, characterized in that: When the washing liquid containing less or no impurity ions is added to the electrolytic cell, the liquid level in the filter bag is made higher than the liquid level outside the filter bag, or the water pressure in the filter bag is increased by using a faster liquid inlet flow rate in the filter bag, so that the liquid in the filter bag seeps out from the inside to the outside, and the solids adhered to the filter bag are squeezed out of the bag by the vibration of the vibrator, so as to accelerate the recovery of the filtering function of the filtering holes of the filter bag.

8. The method for removing soluble impurities according to claim 7, characterized in that: Ion exchange resin pure water equipment is used to remove impurity ions from the washing liquid pumped out during the ionization and impurity removal operation or the washing waste liquid rich in impurity ions obtained after the operation is completed, to obtain a washing liquid containing less or no impurity ions, which is then circulated and added to the electrolytic cell for reuse.

9. The method for removing soluble impurities according to claim 8, characterized in that: Before the ionization and impurity removal operation, the solid material to be washed is mechanically ground or crushed by ultrasonic impact.

10. The method for removing soluble impurities according to claim 9, characterized in that: A liquid suction tube is additionally arranged on at least one electrode outside the filter bag and / or near the electrode, and a slower liquid suction speed or a lower liquid suction frequency is adopted, and / or the liquid suction is performed after the washed material is allowed to settle.

11. The method for removing soluble impurities according to claim 10, characterized in that: In the space area outside the filter bag in the electrolytic cell, an agitator is used to stir the solid-liquid mixture of the washed substance and the washing liquid to accelerate the soluble impurities in the washed substance to leave the washed substance and dissolve into the washing liquid.

12. The method for removing soluble impurities according to claim 11, characterized in that: The solid-liquid mixture of the washed material and the washing liquid is stirred intermittently by a stirrer. The electrolytic power supply is turned off each time stirring is performed, and after stirring stops, the electrolytic power supply is turned on for ionization and impurity removal after the solid matter therein has partially or completely settled.

13. The method for removing soluble impurities according to claim 12, characterized in that: When stirring with an agitator, the electrodes and filter bags are partially or completely lifted away from the liquid surface, giving the solid-liquid mixture formed by the washed material and the washing liquid a larger stirring space.

14. The method for removing soluble impurities according to claim 13, characterized in that: The washing liquid in the electrolytic cell is heated by a hot and cold temperature exchanger.

15. The method for removing soluble impurities according to claim 14, characterized in that: The ionization and impurity removal operation is carried out using an electrolysis voltage that is higher than the electrolyte decomposition voltage value.

16. A device for removing soluble impurities using the method of claim 1, characterized in that: include: An electrolytic cell, an electrolytic anode, an electrolytic cathode and an electrolytic power supply, wherein: An electrolytic anode and an electrolytic cathode are arranged in the electrolytic cell, and the electrolytic anode and the electrolytic cathode are respectively connected to the positive electrode and the negative electrode of the electrolytic power supply; at least one electrolytic anode and / or the electrolytic cathode is wrapped by the filter bag; A vibrator is provided to vibrate the filter bag, and a liquid suction pipe is connected to the outside of the electrolytic cell; the liquid suction port of the liquid suction pipe is arranged in the filter bag, and each filter bag has at least one liquid suction port.

17. The device according to claim 16, characterized in that The electrolytic cell is made of polymer resin material and / or metal coated or wrapped with anti-corrosion insulating material; The electrolytic anode is an insoluble anode, and its surface material in contact with the washing liquid is one or more selected from gold, platinum, titanium-based coating, conductive graphite, titanium, and nickel; the electrolytic cathode is an insoluble cathode, and its surface material in contact with the washing liquid is one or more selected from gold, platinum, titanium, nickel, silver, copper, an alloy containing at least one of the above metals, stainless steel, and conductive graphite.

18. The device according to claim 17, characterized in that The liquid pipette is installed and combined with the electrode as a whole, or the electrode and the liquid pipette are placed in the filter bag in an independent structural form.

19. The device according to claim 18, characterized in that The vibrator is an electric vibrator and / or a pneumatic electric vibrator; the vibrator is closely attached to the filter bag or fixed on a fixed component in contact with the filter bag.

20. The device according to claim 19, characterized in that A solid-liquid separator is added, and the electrolytic cell is connected to the solid-liquid separator through a pipeline and a pump.

21. The device according to claim 20, characterized in that A temporary storage tank is added to temporarily store materials and clean water, or to wash and soak substances; it is connected to at least one container or equipment in the device through a pipeline; An ion exchange resin pure water device is additionally provided, and the ion exchange resin pure water device is connected to at least one container or device in the device by a pipeline.

22. The device according to claim 21, characterized in that A mechanical grinding mill and / or an ultrasonic generator is added to break the solid state of the washed material; the ultrasonic generator is installed in the electrolytic tank or the temporary storage tank for breaking the washed material.

23. The device according to claim 22, characterized in that A filter bag shaping frame is added to the filter bag; the filter bag shaping frame is a frame or box frame made of a hard material that is insoluble in the washing liquid.

24. The device according to claim 23, characterized in that A water adding pipe is added to add washing liquid containing less or no impurity ions to the space inside the filter bag and / or outside the filter bag in the electrolytic cell.

25. The device according to claim 24, characterized in that An exhaust pipe is added to the filter bag shaping frame to collect and treat the waste gas escaping from the filter bag.

26. The device according to claim 25, characterized in that The bottom of the electrolytic cell adopts a funnel-shaped structure.

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