Device and method for dissolving out waste printed circuit board metal through microwave enhanced electrochemistry
阅读说明：本技术 一种微波强化电化学溶出废印刷电路板金属的装置及方法 (Device and method for dissolving out waste printed circuit board metal through microwave enhanced electrochemistry ) 是由 何春林 赵健 李�杰 藤田豊久 韦悦周 苏秀娟 马少健 于 2021-01-04 设计创作，主要内容包括：本发明公开了一种微波强化电化学溶出废印刷电路板金属的装置及方法,该装置包括磁控管、微波反射腔体、环形器、单模波导、微波功率检测计、控制面板、尾气吸收盒、温度变送器、密封盖、溶出反应槽、反应腔、电解槽、连接架、阴电极、阳电极、格栅板、卸料盖、电解液、电解电源和微波屏蔽罩；微波可强化电解产生Cl-2的效率和量,促进反应的进行,微波屏蔽罩、密封盖、反应腔可隔离Cl-2和微波,避免对环境和人体造成危害；尤其是对废印刷电路板的金属粉、镀有金银等稀贵金属的装饰品、稀贵金属催化剂等具有很好的电解浸出特性；本发明强化Cu、Ni、Zn、Au、Ag、Fe、Al、Sn、Pb等金属溶出,浸出率高达98%以上,微波强化整个浸出过程极大缩短了浸出时间。(The invention discloses a device and a method for stripping waste printed circuit board metal by microwave-enhanced electrochemistry, wherein the device comprises a magnetron, a microwave reflection cavity, a circulator, a single-mode waveguide, a microwave power detector, a control panel, a tail gas absorption box, a temperature transmitter, a sealing cover, a stripping reaction tank, a reaction cavity, an electrolytic tank, a connecting frame, a cathode electrode, an anode electrode, a grid plate, a discharging cover, electrolyte, an electrolytic power supply and a microwave shielding cover; microwave-enhanced electrolysis for generating Cl 2 The efficiency and the quantity of the reaction are improved, the microwave shielding cover, the sealing cover and the reaction cavity can isolate Cl 2 And microwave, avoid causing the harm to environment and human body; particularly has good electrolytic leaching characteristics on metal powder of a waste printed circuit board, ornaments plated with rare and noble metals such as gold and silver, rare and noble metal catalysts and the like; the invention strengthens the dissolution of metals such as Cu, Ni, Zn, Au, Ag, Fe, Al, Sn, Pb and the like, and the leaching rate reaches as high asMore than 98 percent, the whole leaching process is strengthened by microwave, and the leaching time is greatly shortened.)
1. A device for electrochemically dissolving out waste printed circuit board metal by microwave reinforcement is characterized in that: including circulator (3), port one and port two of circulator (3) are respectively towards single mode waveguide (4) front and back both ends, the front end fixed mounting of single mode waveguide (4) has magnetron (1), the port three of circulator (3) is connected with microwave reflection cavity (2), fixed mounting has microwave power detector (5) on single mode waveguide (4) at circulator (3) rear, the side of the rear end fixed connection reaction chamber (11) of single mode waveguide (4), bolt fixedly connected with sealed lid (9) is passed through at the top of reaction chamber (11), the through-hole of adaptation installation temperature transmitter (8), negative electrode (13), positive electrode (14) is seted up perpendicularly on sealed lid (9), tail gas absorption box (7) have been placed to the top surface of sealed lid (9), the last side cover of sealed lid (9) is equipped with microwave shield cover (19), the inside of reaction chamber (11) is equipped with electrolysis trough (12), the internal thread through-hole of threaded connection unloading lid (16) is seted up to the bottom of electrolysis trough (12), there is dissolution reaction tank (10) inside of electrolysis trough (12) through link (121) fixed mounting, the inside slidable mounting that dissolves out reaction tank (10) has grid board (15), electrolyte (17) are held to the inside of electrolysis trough (12), negative electrode (13), positive electrode (14) electric connection electrolysis power (18), temperature transmitter (8), microwave power detector (5), magnetron (1) electric connection control panel (6).
2. The apparatus of claim 1, wherein the apparatus further comprises: the single-mode waveguide (4) is of a hollow metal pipe structure with a closed front end, and an internal thread through hole for fixedly mounting the magnetron (1) and the microwave power detector (5) is formed in the side face of the single-mode waveguide (4).
3. The apparatus of claim 1, wherein the apparatus further comprises: the terminal through-hole of welded connection single mode waveguide (4) is seted up to the preceding terminal surface of reaction chamber (11), reaction chamber (11) are top open-ended square groove structure, sealed lid (9) are the same square plate structure of length width and reaction chamber (11), the through-hole of adaptation installation temperature transmitter (8) is seted up to the top surface of microwave shield cover (19).
4. The apparatus of claim 1, wherein the apparatus further comprises: the height of the electrolytic cell (12) is smaller than that of the reaction cavity (11), one end of the connecting frame (121) is connected with the inner wall of the electrolytic cell (12) in a welding mode, the other end of the connecting frame (121) fixes the outer side face of the dissolution reaction tank (10) through a pipe clamp, and the dissolution reaction tank (10) is of a round pipe type structure with an open top end and made of glass/plastic/conventional glass/quartz glass.
5. The apparatus of claim 1, wherein the apparatus further comprises: the bottom end of the dissolution reaction tank (10) is provided with a notch with the diameter of 1-10cm smaller than that of the grid plate (15), the electrode bar of the anode electrode (14) passes through the grid plate (15), the interior of the dissolution reaction tank (10) above the grid plate (15) is provided with waste printed circuit fragments, the anode electrode (14) and the cathode electrode (13) are one of a platinum sheet electrode, a graphite electrode and a titanium electrode, the area of the anode electrode (14) is 3X 3cm, the area of the cathode electrode (13) is 1X 1cm, the thickness of the anode electrode (14) and the cathode electrode (13) is 0.05cm, the straight-line distance between the anode electrode (14) and the cathode electrode (13) is 3-5cm, the electrolyte (17) is a solution/NaCl aqueous solution/hydrochloric acid solution/ferric chloride solution/cupric chloride solution/H prepared by NaCl and inorganic acid according to a certain proportion.2O2And (3) solution.
6. The apparatus of claim 1, wherein the apparatus further comprises: the conduction direction of the circulator (3) is from a port one to a port two, from the port two to the port three, and from the port three to the port one.
7. The apparatus of claim 1, wherein the apparatus further comprises: the tail gas absorption box (7) is a box body containing NaOH solution.
8. The apparatus of claim 1, wherein the apparatus further comprises: the positive electrode (14) is arranged at the bottom of the grid plate (15) and is fixedly connected with the grid plate (15), and the grid plate (15) is of a circular plate type structure made of organic glass, plastic, ceramic and the like and with the aperture of 1-2 mm.
9. The apparatus of claim 1, wherein the apparatus further comprises: the discharge cover (16) is positioned vertically below the digestion reaction tank (10).
10. A method for electrochemically dissolving out waste printed circuit board metal by microwave reinforcement is characterized in that: apparatus for the enhanced electrochemical digestion of spent printed circuit board metal using microwaves as claimed in any one of claims 1 to 9, comprising the steps of:
(1) stripping components on the waste printed circuit board, cutting the pretreated waste printed circuit board into a plurality of square small blocks by using a cutting machine, and putting the square small blocks into a crusher for crushing, wherein the waste printed circuit board is processed into a powder sample;
(2) preparing an electrolyte (17);
(3) weighing a proper amount of powder sample, placing the powder sample above a grid plate (15) in a dissolution reaction tank (10), and putting an anode into an electrolytic tank (12) filled with electrolyte (17) through the grid plate (15);
(4) switching on a power supply to perform microwave reinforced electrolysis, setting the current of a direct current power supply to be 0.5-1.5A and the microwave power to be 100-1400W, performing electrolysis for 15-30min, taking out a sample, filtering, drying, weighing, testing and analyzing the metal content, and calculating the metal leaching rate.
Technical Field
The invention belongs to the technical field of metal extraction devices, and particularly relates to a device and a method for microwave-enhanced electrochemical dissolution of waste printed circuit board metal.
Background
Rare and precious metals are used as an important material resource and widely applied to the fields of aerospace, national defense and military industry, electronic information, new materials, chemical industry, equipment manufacturing and the like, but with the rapid development of modern industry, the resource development speed is high, the total amount of resources is reduced day by day, and the problem of rare and precious metal resources is particularly prominent, so that the recovery and cyclic utilization of secondary resources become the direction of sustainable development, and by taking 1t of waste printed circuit boards as an example, 400g of gold, 200kg of copper and 700kg of polyester can be extracted when the utilization rate reaches 99 percent.
At present, the post-treatment method comprises the common traditional methods such as incineration method, shaking table separation method, wet leaching and the like, and improved method, new technical method, such as mild extraction technology, microorganism leaching technology, etc., the method adopts the medicaments with strong toxicity such as sodium cyanide, potassium cyanide and the like for dissolving out rare and precious metals, not only is the environment friendly, the microwave-assisted leaching and the electrochemical leaching are characterized by high efficiency, low energy consumption, environmental friendliness and the like, the electrochemical extraction method not only can treat nonferrous metals and rare and precious metals in waste printed circuit boards, but also has the advantages of high electric energy utilization rate, environmental friendliness, no pollution of medicaments and the like, when the microwave and the electrochemistry are jointly applied, the microwave realizes the activation effect on electrodes, the mass transfer rate is improved, the reaction is promoted to be carried out integrally, this undoubtedly provides a new technical approach to the recovery of valuable metals from waste printed circuit boards.
Disclosure of Invention
To solve the problems set forth in the background art described above. The invention provides a device for electrochemically dissolving out waste printed circuit board metal by microwave enhancement, and the microwave generated by a magnetron can enhance electrolysis to generate Cl2The efficiency and the quantity of the reaction are improved, the microwave shielding cover, the sealing cover and the reaction cavity can isolate Cl2And microwave, avoid causing the harm to environment and human body; especially has good electrolytic leaching property for metal powder of waste printed circuit boards, ornaments plated with rare noble metals such as gold and silver, rare noble metal catalysts and the like.
In order to achieve the purpose, the invention provides the following technical scheme: the utility model provides a device that useless printed circuit board metal is dissolved out to microwave reinforcement electrochemistry, includes the circulator, port one and the port two of circulator are towards single mode waveguide's front and back both ends respectively, single mode waveguide's front end fixed mounting has the magnetron, the port three of circulator is connected with the microwave reflection cavity, fixed mounting has the microwave power detector on the single mode waveguide at circulator rear, the side of single mode waveguide's rear end fixed connection reaction chamber, the top of reaction chamber is through bolt fixedly connected with sealed lid, the through-hole of adaptation installation temperature transmitter, negative pole, positive pole is seted up perpendicularly to sealed covering, tail gas absorption box has been placed to the top surface of sealed lid, the last side cover of sealed lid is equipped with the microwave shield cover, the inside of reaction chamber is equipped with the electrolysis trough, the internal thread through-hole of threaded connection unloading lid is seted up to the bottom of electrolysis trough, the inside of electrolysis trough is passed through link fixed mounting and is dissolved out the reaction tank, the inside slidable mounting who dissolves out the reaction tank has the grid board, the inside appearance of electrolysis trough is equipped with electrolyte, negative electrode, positive electrode electric connection electrolysis power, temperature transmitter, microwave power detector, magnetron electric connection control panel.
Preferably, the single-mode waveguide is a hollow metal tube structure with a closed front end, and an internal thread through hole for fixedly mounting a magnetron and a microwave power detector is formed in the side surface of the single-mode waveguide; the microwave power detector can detect the reflection of the microwave transmitted by the circulator and the single-mode waveguide.
Preferably, the front end face of the reaction chamber is provided with a through hole welded to the tail end of the single-mode waveguide, the reaction chamber is of a square groove structure with an opening at the top end, the sealing cover is of a square plate structure with the length and width identical to those of the reaction chamber, and the top face of the microwave shielding cover is provided with a through hole adapted to be provided with a temperature transmitter; the sealing cover and the reaction cavity can play a role in sealing, so that Cl generated in the electrolytic process is avoided2When the microwave is volatilized to the environment, the microwave shielding cover can play a shielding role and prevent the microwave from leaking.
Preferably, the height of the electrolytic cell is less than that of the reaction cavity, one end of the connecting frame is welded and connected with the inner wall of the electrolytic cell, the other end of the connecting frame is fixed on the outer side surface of the dissolution reaction tank through a pipe clamp, and the dissolution reaction tank is of a round pipe type structure with an open top end and made of glass/plastic/conventional glass/quartz glass; the dissolution reaction tank is corrosion-resistant and easy to clean, and can be used in an electrolysis environment for a long time.
Preferably, the bottom end of the dissolution reaction tank is provided with a notch with the diameter being 1-10cm smaller than that of the grid plate, an electrode rod of the anode electrode penetrates through the grid plate, waste printed circuit fragments are arranged inside the dissolution reaction tank above the grid plate, the anode electrode and the cathode electrode are platinum sheet electrodes, graphite electrodes and titanium electrodes, the area of the anode electrode is 3 x 3cm, the area of the cathode electrode is 1 x 1cm, the thicknesses of the anode electrode and the cathode electrode are 0.05cm, the linear distance between the anode electrode and the cathode electrode is 3-5cm, and the electrolyte is a solution/NaCl aqueous solution/hydrochloric acid solution/ferric chloride solution/copper chloride solution/H prepared by NaCl and inorganic acid in proportion2O2A solution; after the anode and cathode electrodes are electrified, the waste printed circuit board powder metal immersed in the electrolyte is electrolyzed.
Preferably, the conduction direction of the circulator is from the port one to the port two, from the port two to the port three, and from the port three to the port one; after the microwave is started, the microwave can strengthen the electrolysis to generate Cl2And due to Cl2The waste printed circuit board powder is floated and stirred, so that the reaction can be promoted, and the extraction effect is improved.
Preferably, the first and second liquid crystal materials are,the tail gas absorption box is a box body containing NaOH solution; cl produced by electrolysis of electrolyte2The sodium chloride solution generated by the reaction of the gas and NaOH in the tail gas absorption box can be used as electrolyte for recycling.
Preferably, the positive electrode is arranged below the grid plate and is fixedly connected with the grid plate, and the grid plate is of a circular plate type structure with the aperture of 1-2mm and is made of organic glass/plastic/ceramic and the like; the grid plate can play a role in isolating and placing waste printed circuit fragments, and the grid plate can move up and down along with the anode electrode, so that subsequent unloading is facilitated.
Preferably, the discharge cover is positioned vertically below the dissolution reaction tank; the operator can unscrew the discharge cover to discharge the electrolytic solution material and collect the electrolytic deposition metal.
A method for electrochemically dissolving out waste printed circuit board metal by microwave reinforcement comprises the following steps:
(1) stripping components on the waste printed circuit board, cutting the pretreated waste printed circuit board into a plurality of square small blocks by using a cutting machine, and putting the square small blocks into a crusher for crushing, wherein the waste printed circuit board is processed into a powder sample;
(2) preparing electrolyte;
(3) weighing a proper amount of powder sample, placing the powder sample above a grid plate in a dissolution reaction tank, and putting an anode into an electrolytic tank filled with electrolyte through the grid plate;
(4) switching on a power supply to perform microwave reinforced electrolysis, setting the current of a direct current power supply to be 0.5-1.5A and the microwave power to be 100-1400W, performing electrolysis for 15-30min, taking out a sample, filtering, drying, weighing, testing and analyzing the metal content, and calculating the metal leaching rate.
Compared with the prior art, the invention has the beneficial effects that: the microwave power detector can detect the microwave reflection condition transmitted by the circulator and the single-mode waveguide; the sealing cover and the reaction cavity can play a role in sealing, so that Cl generated in the electrolytic process is avoided2When the microwave is volatilized into the environment, the microwave shielding cover can play a shielding role to prevent the microwave from leaking; the dissolution reaction tank is corrosion-resistant and easy to clean, and can be used in an electrolytic environment for a long time; after the anode and cathode are electrified, electricity is suppliedDe-immersing the waste printed circuit board powder metal in an electrolyte; after the microwave is started, the microwave can strengthen the electrolysis to generate Cl2And due to Cl2The waste printed circuit board powder is floated and stirred, so that the reaction can be promoted, and the extraction effect is improved; cl produced by electrolysis of electrolyte2The sodium chloride solution generated by the reaction of the gas and NaOH in the tail gas absorption box can be used as electrolyte for recycling; the grid plate can play a role in isolating and placing waste printed circuit fragments, and the grid plate can move up and down along with the positive electrode, so that subsequent unloading is facilitated; the operator can unscrew the discharge cover to discharge the electrolytic solution material and collect the electrolytic deposition metal. The invention strengthens the dissolution of metals such as Cu, Ni, Zn, Au, Ag, Fe, Al, Sn, Pb and the like, the leaching rate is up to more than 98 percent, and the whole leaching process is strengthened by microwaves, so that the leaching time is greatly shortened.
The parts of the device not involved are the same as or can be implemented using prior art.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a schematic structural view of the present invention;
in the figure: 1. a magnetron; 2. a microwave reflective cavity; 3. a circulator; 4. a single mode waveguide; 5. a microwave power detector; 6. a control panel; 7. a tail gas absorption box; 8. a temperature transmitter; 9. a sealing cover; 10. a dissolution reaction tank; 11. a reaction chamber; 12. an electrolytic cell; 121. a connecting frame; 13. a cathode electrode; 14. an anode electrode; 15. a grid plate; 16. a discharge cover; 17. an electrolyte; 18. an electrolysis power supply; 19. a microwave shield.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Referring to fig. 1, the present invention provides the following technical solutions: the utility model provides a device that useless printed circuit board metal is dissolved out to microwave reinforcement electrochemistry, includes circulator 3, port one and port two of circulator 3 are towards single mode waveguide 4 front and back both ends respectively, single mode waveguide 4's front end fixed mounting has magnetron 1, circulator 3's port three is connected with microwave reflection cavity 2, fixed mounting has microwave power detector 5 on the single mode waveguide 4 at circulator 3 rear, single mode waveguide 4's rear end fixed connection reaction chamber 11's side, bolt fixedly connected with sealed lid 9 is passed through at reaction chamber 11's top, the through-hole of adapter installation temperature transmitter 8, negative electrode 13, positive electrode 14 has been seted up perpendicularly on the sealed lid 9, tail gas absorption box 7 has been placed to the top surface of sealed lid 9, the last side cover of sealed lid 9 is equipped with microwave shielding cover 19, reaction chamber 11's inside is equipped with electrolysis trough 12, the bottom of the electrolytic cell 12 is provided with an internal thread through hole in which a discharging cover 16 is in threaded connection, the inside of the electrolytic cell 12 is fixedly provided with a dissolution reaction tank 10 through a connecting frame 121, the inside of the dissolution reaction tank 10 is provided with a grid plate 15 in a sliding manner, the inside of the electrolytic cell 12 is provided with electrolyte 17, a cathode electrode 13 and an anode electrode 14 are electrically connected with an electrolytic power supply 18, and a temperature transmitter 8, a microwave power detector 5 and a magnetron 1 are electrically connected with a control panel 6.
Specifically, the single-mode waveguide 4 is a hollow metal tube structure with a closed front end, and an internal thread through hole for fixedly mounting the magnetron 1 and the microwave power detector 5 is formed in the side surface of the single-mode waveguide 4; the microwave power detector 5 can detect the reflection of the microwave transmitted through the circulator 3 and the single-mode waveguide 4.
Specifically, a through hole welded to the end of the single-mode waveguide 4 is formed in the front end face of the reaction chamber 11, the reaction chamber 11 is of a square groove structure with an opening at the top end, the sealing cover 9 is of a square plate structure with the length and width being the same as those of the reaction chamber 11, and a through hole adapted to mount the temperature transmitter 8 is formed in the top face of the microwave shielding cover 19; the sealing cover 9 and the reaction chamber 11 can be taken upTo the sealing effect and avoid Cl generated in the electrolytic process2When the microwave is volatilized into the environment, the microwave shielding case 19 can play a role in shielding, and the microwave is prevented from being leaked.
Specifically, the height of the electrolytic cell 12 is less than that of the reaction chamber 11, one end of the connecting frame 121 is welded to the inner wall of the electrolytic cell 12, the other end of the connecting frame 121 is fixed to the outer side surface of the dissolution reaction tank 10 through a pipe clamp, and the dissolution reaction tank 10 is a round pipe structure with an open top end made of glass/plastic/conventional glass/quartz glass; the dissolution reaction tank 10 is corrosion resistant and easy to clean, and can be used in an electrolysis environment for a long time.
Specifically, a notch with a diameter smaller than the diameter of 1-10cm of the grid plate 15 is formed in the bottom end of the leaching reaction tank 10, an electrode rod of the anode electrode 14 penetrates through the grid plate 15, waste printed circuit fragments are arranged inside the leaching reaction tank 10 above the grid plate 15, the anode electrode 14 and the cathode electrode 13 are one of a platinum sheet electrode, a graphite electrode and a titanium electrode, the area of the anode electrode 14 is 3 × 3cm, the area of the cathode electrode 13 is 1 × 1cm, the thicknesses of the anode electrode 14 and the cathode electrode 13 are 0.05cm, and the linear distance between the anode electrode 14 and the cathode electrode 13 is 3-5 cm.
Specifically, the conduction direction of the circulator 3 is from port one to port two, from port two to port three, and from port three to port one; after the microwave is started, the microwave can strengthen the electrolysis to generate Cl2And due to Cl2The waste printed circuit board powder is floated and stirred, so that the reaction can be promoted, and the extraction effect is improved.
Specifically, the tail gas absorption box 7 is a box body containing a NaOH solution; cl produced by electrolysis of electrolyte 172The sodium chloride solution generated by the reaction of the gas and NaOH in the tail gas absorption box 7 can be used as electrolyte for recycling.
Specifically, the anode electrode 14 is arranged below the grid plate 15 and fixedly connected with the grid plate 15, and the grid plate 15 is a circular plate type structure made of organic glass/plastic/ceramic and the like and having a pore diameter of 1-2 mm; the grid plate 15 can play a role in isolating and placing waste printed circuit fragments, and the grid plate 15 can move up and down along with the anode electrode 14, so that subsequent unloading is facilitated.
Specifically, the discharge cover 16 is positioned vertically below the dissolution reaction tank 10; the operator can screw down the discharge cap 16 to discharge the electrolytic solution material and collect the electrodeposited metal.
A method for electrochemically dissolving out waste printed circuit board metal by microwave reinforcement comprises the following steps:
(1) stripping components on the waste printed circuit board by using tools such as an electric welding pen, a pair of pliers, scissors and the like, cutting the pretreated waste printed circuit board into a plurality of square small blocks by using a cutting machine, and crushing the square small blocks in a crusher to process the waste printed circuit board into powder samples;
(2) preparing electrolyte, namely preparing 500ml of electrolyte solution from 80ml of concentrated sulfuric acid, 20ml of 37.5 mass percent hydrogen peroxide and 15g of sodium chloride;
(3) weighing 15g of powder sample, placing the powder sample above a grid plate in a dissolution reaction tank, and putting an anode into an electrolytic tank filled with electrolyte through the grid plate;
(4) switching on a power supply to perform microwave reinforced electrolysis, setting the current of a direct current power supply to be 0.6A and the microwave power to be 100W, performing electrolysis for 20min, taking out a sample, filtering, drying, weighing, testing and analyzing the metal content, and calculating the metal leaching rate.
Weighing 1g of dried waste printed circuit board metal powder, and detecting the content of various metal ions in the metal powder; the result shows that the leaching rate of metals such as Cu, Ni, Zn, Au, Ag, Fe, Al, Sn, Pb and the like is as high as more than 98-99%.
Example 2
Referring to fig. 1, the present invention provides the following technical solutions: the utility model provides a device that useless printed circuit board metal is dissolved out to microwave reinforcement electrochemistry, includes circulator 3, port one and port two of circulator 3 are towards single mode waveguide 4 front and back both ends respectively, single mode waveguide 4's front end fixed mounting has magnetron 1, circulator 3's port three is connected with microwave reflection cavity 2, fixed mounting has microwave power detector 5 on the single mode waveguide 4 at circulator 3 rear, single mode waveguide 4's rear end fixed connection reaction chamber 11's side, bolt fixedly connected with sealed lid 9 is passed through at reaction chamber 11's top, the through-hole of adapter installation temperature transmitter 8, negative electrode 13, positive electrode 14 has been seted up perpendicularly on the sealed lid 9, tail gas absorption box 7 has been placed to the top surface of sealed lid 9, the last side cover of sealed lid 9 is equipped with microwave shielding cover 19, reaction chamber 11's inside is equipped with electrolysis trough 12, the bottom of the electrolytic cell 12 is provided with an internal thread through hole in which a discharging cover 16 is in threaded connection, the inside of the electrolytic cell 12 is fixedly provided with a dissolution reaction tank 10 through a connecting frame 121, the inside of the dissolution reaction tank 10 is provided with a grid plate 15 in a sliding manner, the inside of the electrolytic cell 12 is provided with electrolyte 17, a cathode electrode 13 and an anode electrode 14 are electrically connected with an electrolytic power supply 18, and a temperature transmitter 8, a microwave power detector 5 and a magnetron 1 are electrically connected with a control panel 6.
Specifically, the single-mode waveguide 4 is a hollow metal tube structure with a closed front end, and an internal thread through hole for fixedly mounting the magnetron 1 and the microwave power detector 5 is formed in the side surface of the single-mode waveguide 4; the microwave power detector 5 can detect the reflection of the microwave transmitted through the circulator 3 and the single-mode waveguide 4.
Specifically, a through hole welded to the end of the single-mode waveguide 4 is formed in the front end face of the reaction chamber 11, the reaction chamber 11 is of a square groove structure with an opening at the top end, the sealing cover 9 is of a square plate structure with the length and width being the same as those of the reaction chamber 11, and a through hole adapted to mount the temperature transmitter 8 is formed in the top face of the microwave shielding cover 19; the sealing cover 9 and the reaction cavity 11 can play a role in sealing, so that Cl generated in the electrolytic process is avoided2When the microwave is volatilized into the environment, the microwave shielding case 19 can play a role in shielding, and the microwave is prevented from being leaked.
Specifically, the height of the electrolytic cell 12 is less than that of the reaction chamber 11, one end of the connecting frame 121 is welded to the inner wall of the electrolytic cell 12, the other end of the connecting frame 121 is fixed to the outer side surface of the dissolution reaction tank 10 through a pipe clamp, and the dissolution reaction tank 10 is a round pipe structure with an open top end made of glass/plastic/conventional glass/quartz glass; the dissolution reaction tank 10 is corrosion resistant and easy to clean, and can be used in an electrolysis environment for a long time.
Specifically, a notch with a diameter smaller than the diameter of 1-10cm of the grid plate 15 is formed in the bottom end of the leaching reaction tank 10, an electrode rod of the anode electrode 14 penetrates through the grid plate 15, waste printed circuit fragments are arranged inside the leaching reaction tank 10 above the grid plate 15, the anode electrode 14 and the cathode electrode 13 are one of a platinum sheet electrode, a graphite electrode and a titanium electrode, the area of the anode electrode 14 is 3 × 3cm, the area of the cathode electrode 13 is 1 × 1cm, the thicknesses of the anode electrode 14 and the cathode electrode 13 are 0.05cm, and the linear distance between the anode electrode 14 and the cathode electrode 13 is 3-5 cm.
Specifically, the conduction direction of the circulator 3 is from port one to port two, from port two to port three, and from port three to port one; after the microwave is started, the microwave can strengthen the electrolysis to generate Cl2And due to Cl2The waste printed circuit board powder is floated and stirred, so that the reaction can be promoted, and the extraction effect is improved.
Specifically, the tail gas absorption box 7 is a box body containing a NaOH solution; cl produced by electrolysis of electrolyte 172The sodium chloride solution generated by the reaction of the gas and NaOH in the tail gas absorption box 7 can be used as electrolyte for recycling.
Specifically, the anode electrode 14 is arranged below the grid plate 15 and fixedly connected with the grid plate 15, and the grid plate 15 is a circular plate type structure made of organic glass/plastic/ceramic and the like and having a pore diameter of 1-2 mm; the grid plate 15 can play a role in isolating and placing waste printed circuit fragments, and the grid plate 15 can move up and down along with the anode electrode 14, so that subsequent unloading is facilitated.
Specifically, the discharge cover 16 is positioned vertically below the dissolution reaction tank 10; the operator can screw down the discharge cap 16 to discharge the electrolytic solution material and collect the electrodeposited metal.
A method for electrochemically dissolving out waste printed circuit board metal by microwave reinforcement comprises the following steps:
(1) stripping components on the waste printed circuit board by using tools such as an electric welding pen, a pair of pliers, scissors and the like, cutting the pretreated waste printed circuit board into a plurality of square small blocks by using a cutting machine, and crushing the square small blocks in a crusher to process the waste printed circuit board into powder samples;
(2) preparing electrolyte, namely preparing 500ml of electrolyte solution from 50ml of concentrated sulfuric acid, 30ml of hydrogen peroxide with the mass fraction of 37.5% and 30g of copper chloride;
(3) weighing 15g of powder sample, placing the powder sample above a grid plate in a dissolution reaction tank, and putting an anode into an electrolytic tank filled with electrolyte through the grid plate;
(4) switching on a power supply to perform microwave reinforced electrolysis, setting the current of a direct current power supply to be 0.8A and the microwave power to be 150W, performing electrolysis for 20min, taking out a sample, filtering, drying, weighing, testing and analyzing the metal content, and calculating the metal leaching rate.
Weighing 1g of dried waste printed circuit board metal powder, and detecting the content of various metal ions in the metal powder; the result shows that the leaching rate of metals such as Cu, Ni, Zn, Au, Ag, Fe, Al, Sn, Pb and the like is as high as more than 99 percent.
The working principle and the using process of the invention are as follows:
taking Cu as an example, the principle of electroleaching metals is analyzed:
the reactions that occur at the electrodes after electrolytic energization are as follows:
anode: 2Cl-==Cl2+2e-
Cathode: cu2++2e-==Cu
Reaction of electrolytically generated chlorine in solution:
Cl2(g)== Cl2(aq)
Cl2(aq)+H2O==HCl+HOCl
Cl2(aq)+Cl-== Cl3 -
reaction of the waste printed circuit board Cu in solution:
Cu+Cl2(aq)== Cu2++2Cl-
Cu+ Cl3-== Cu2++3Cl-
Cu2+ + Cu = 2Cu+
Cu + H2O2 + 2H+ == Cu2+ + 2H2O
Cu+ +nCl-==CuCln (n-1)-
2CuCln (n-1)- +2H+ + H2O2 == 2Cu2+ + 2H2O +2nCl-
2Cu + 2H+ + 4Cl- + H2O2 == 2[Cu(Cl2)]- + 2H2O
Cu + 2H+ + 4Cl- + H2O2 == [Cu(Cl4)]- + 2H2O
cl produced by electrolysis2、 Cl3 -Can react and dissolve out Cu in the waste circuit board2+Further copper oxide promotes leaching to obtain Cu+With Cl-Complex reaction is carried out to form complex ion CuCln (n-1)-And is stably leached out. Complex ion CuCln (n -1)-The reaction of the formula for oxidation may also be continued. Cl-And Cu produced2+Can accelerate the leaching of metal copper from the waste circuit board, and the microwave can accelerate Cl in the electrolysis process2And metal leaching reaction process.
The use process comprises the following steps: an operator firstly passes an electrode wire of the anode 14 through the grid plate 15 to enable the anode 14 to be arranged below the grid plate 15, and fixedly connects the anode 14 with the grid plate 15 by using a bandage or other tools, then horizontally puts the grid plate 15 into the bottom of the dissolution reaction tank 10, and then fixedly installs the dissolution reaction tank 10 inside the electrolytic tank 12 by using a pipe clamp;
then, an operator slowly pours the prepared electrolyte 17 into the electrolytic tank 12, electrode wires of the cathode electrode 13 and the anode electrode 14 penetrate through holes formed in the sealing cover 9, the sealing cover 9 is fixedly connected with the reaction cavity 11 by using bolts, then the electrolytic power supply 18, the cathode electrode 13 and the anode electrode 14 are electrically connected, then the microwave shielding cover 19 is covered above the sealing cover 9, the probe of the temperature transmitter 8 is vertically inserted into the through holes in the microwave shielding cover 19 and the sealing cover 9, and the bottom end of the probe of the temperature transmitter 8 is immersed into the electrolyte 17;
starting magnetron 1 via control panel 6, checking microwave leakage, starting electrolysis power supply 18 after microwave leakage detector detects no microwave leakageIn the microwave reinforced electrolysis process, the microwaves generated by the magnetron 1 enter the electrolytic tank 12 through the port I to the port II of the circulator 3 under the guidance of the single-mode waveguide 4, and the reinforced cathode electrode 13 and the reinforced anode electrode 14 are electrolyzed to generate Cl2Efficiency and amount of (1), generation of Cl2The floating force of the floating body stirs the waste PCB powder and the microwave enhances the reaction, and the volatilized Cl2The sodium chloride solution generated by the reaction of the sodium chloride solution and NaOH in the tail gas absorption box 7 can be recycled as electrolyte, in the electrolysis process, a microwave reflection signal detected by the microwave power detector 5 and a temperature value of the electrolyte 17 detected by the temperature transmitter 8 are sent to the control panel 6 for processing, and an operator controls process conditions through the control panel 6;
after the reaction is finished, the operator closes the power supplies of the magnetron 1, the cathode electrode 13 and the anode electrode 14, takes the microwave shielding cover 19 down, takes out the tail gas absorption box 7, removes the sealing cover 9, siphons the electrolyte 17 by using a silica gel hose, then takes out the dissolution reaction tank 10 after disassembly, takes out the waste materials in the dissolution reaction tank 10, then the operator can take out the electrolytic tank 12 only with the rest of the electrodeposited metal from the reaction cavity 11, then opens the discharge cover 16 at the bottom of the electrolytic tank 12, and collects the electrodeposited metal.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
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