1. A method for circularly regenerating copper by acid electrolysis without chlorine gas is characterized in that: the method comprises the following steps:

step 1: carrying out electrolytic copper extraction in a chlorine-free acid electrolytic copper extraction circulating regeneration device, firstly installing a cuprous CU + ion concentration detection sensor at an anolyte outlet of a special anode plate of an integrated ionic membrane composite anode plate structure, connecting the sensor with a variable-frequency circulating pump through a controller, and adjusting the flow rate of the circulating pump according to the cuprous CU-ion concentration value detected by the anolyte outlet in real time;

step 2: when the content of cuprous (CU +) ions is less than 2g/L, the flow rate of the anolyte in the polar plate is increased, when the content of CU-10g is more than or equal to 2g/L, the content of CU-2 is more than or equal to 10g/L, the flow rate of the anolyte in the polar plate is kept unchanged, and the content of CU-10 g/L reduces the flow rate of the anolyte in the polar plate;

and step 3: a cuprous CU + ion concentration detection sensor is arranged at an anolyte inlet of a special anode plate of the integrated ionic membrane composite anode plate structure and is connected with an electrolytic copper extraction rectifier through a controller, and when the cuprous CU + ion concentration at the anode inlet is between 6 and 20g/L, the output current of the rectifier is kept at 500A;

and 4, step 4: when the concentration of cuprous CU + ions at the anode inlet is less than or equal to 5 g/h, reducing the current of the rectifier; when the concentration of cuprous CU + ions at the anode inlet is less than or equal to 2g/L, the current output current of the rectifier is adjusted to be zero, and when the concentration of cuprous CU + ions at the anode inlet is more than or equal to 20g/L, the current output current of the rectifier is increased to 700A;

and 5: collect the monovalent cuprous CU + ion concentration of anolyte entry and export of the special anode plate of integrated ionic membrane composite anode plate structure through the controller, real-time coordinated adjustment frequency conversion circulating pump and electrolysis copper extraction rectifier's flow and current size guarantee that there is certain monovalent cuprous CU + ion in the special anode plate runner of integrated ionic membrane composite anode plate structure, restrain the electrochemical reaction that positive pole district chloridion becomes chlorine.

2. The method for circularly regenerating the acid electrolysis copper extraction without chlorine gas as claimed in claim 1, characterized in that: the chlorine-free acid electrolysis copper-extraction recycling device comprises a working panel (1), wherein a rectifier (4) is arranged on the front end face of the working panel (1), a frequency conversion circulating pump (8), an anode plate (2) and a controller (6) are arranged on one side of the rectifier (4), an anolyte conveying pipe (9) and an anolyte discharge pipe (10) are respectively arranged on the liquid inlet end and the liquid outlet end of the anode plate (2), one ends of the anolyte conveying pipe (9) and the anolyte discharge pipe (10) are respectively connected with the outlet and the inlet of the frequency conversion circulating pump (8) in a sealing manner, a first concentration sensor (11) and a second concentration sensor (12) are respectively arranged on the anolyte conveying pipe (9) and the anolyte discharge pipe (10), and the first concentration sensor (11) and the second concentration sensor (12) are respectively installed with the anolyte conveying pipe (9) and the anolyte discharge pipe (10) in a sealing manner by flanges, and a pipeline pressing block (13) is arranged on the outer walls of the anolyte conveying pipe (9) and the anolyte discharge pipe (10), and a frame connecting plate (14) is arranged below the pipeline pressing block (13).

3. The method for circularly regenerating the acid electrolysis copper extraction without chlorine gas as claimed in claim 2, characterized in that: the upper end of anode plate (2) is provided with installation suspension (3), and installs suspension (3) and work panel (1) fixed mounting through the screw, all be provided with installation bedplate (5) on the rear end face of rectifier (4) and controller (6), and install bedplate (5) and rectifier (4) and controller (6) integrated into one piece setting, install end cap bolt (7) in the mounting hole of installation bedplate (5) and work panel (1) inside.

4. The method for circularly regenerating the acid electrolysis copper extraction without chlorine gas as claimed in claim 3, characterized in that: be provided with uide bushing (24) and screw insert sleeve (25) on the outer wall of end cap bolt (7), and uide bushing (24) and screw insert sleeve (25) integrated into one piece set up, the one end of screw insert sleeve (25) is provided with expansion opening (27), and expands opening (27) and screw insert sleeve (25) integrated into one piece set up, the inside of screw insert sleeve (25) and uide sleeve (24) is provided with drive screw (26), drive screw (26) and screw insert sleeve (25) screw thread swing joint, and drive screw (26) and end cap bolt (7) integrated into one piece set up.

5. The method for cyclic regeneration of copper by acid electrolysis without chlorine gas as claimed in claim 4, wherein: one end of the transmission screw rod (26) is provided with a distraction end (28), the distraction end (28) and the transmission screw rod (26) are integrally formed, one end of the guide sleeve (24) is provided with a closed ring plate (23), the closed ring plate (23) and the guide sleeve (24) are integrally formed, and the inner caliber of the closed ring plate (23) is smaller than the size of the end cap bolt (7).

6. The method for circularly regenerating the acid electrolysis copper extraction without chlorine gas as claimed in claim 2, characterized in that: the both ends of frame fishplate bar (14) all are provided with laminating end seat (15), and laminating end seat (15) sets up with frame fishplate bar (14) integrated into one piece, install fastening bolt (16) in the inside through-hole of laminating end seat (15), and laminating end seat (15) pass through fastening bolt (16) and work panel (1) fixed connection, be provided with fibre cloth cover (17) on the hookup location of pipeline briquetting (13) and two laminating end seats (15), the both ends of fibre cloth cover (17) all are provided with connection end (18), and connect end (18) through screw and pipeline briquetting (13) and laminating end seat (15) fixed connection.

7. The method for circularly regenerating the acid electrolysis copper extraction without chlorine gas as claimed in claim 6, characterized in that: be provided with steel wire stay (19), adjacent two on the inner wall of fibre cloth cover (17) through activity spiale (20) swing joint between steel wire stay (19), be provided with return spring (21) on the central point of fibre cloth cover (17) puts, the both ends of return spring (21) all are provided with spring connecting seat (22), and spring connecting seat (22) and return spring (21) integrated into one piece set up, spring connecting seat (22) are through screw and connection end (18) fixed connection.

8. The method for circularly regenerating the acid electrolysis copper extraction without chlorine gas as claimed in claim 2, characterized in that: the output end of the rectifier (4) is electrically connected with the input end of the controller (6), and the output end of the controller (6) is electrically connected with the input ends of the variable-frequency circulating pump (8), the first concentration sensor (11) and the second concentration sensor (12).

9. The method for circularly regenerating the acid electrolysis copper extraction without chlorine gas as claimed in claim 1, characterized in that: the first concentration sensor (11) is a cuprous CU + ion concentration detection sensor, and the second concentration sensor (12) is a cuprous CU-ion concentration detection sensor.

10. The method for circularly regenerating the acid electrolysis copper extraction without chlorine gas as claimed in claim 1, characterized in that: the anode plate (2) is a special anode plate with an integrated ionic membrane composite anode plate structure.

Background

The electrolytic copper extraction is that crude copper is made into a thick plate in advance to be used as an anode, pure copper is made into a thin plate to be used as an anode, mixed liquid of sulfuric acid and copper sulfate is used as electrolyte, after the power is turned on, copper is dissolved into copper ions from the anode and moves to the anode, electrons are obtained after the copper ions reach the anode, the pure copper is separated out from the anode, and impurities in the crude copper, such as iron, zinc and the like which are more active than the copper, can be dissolved into ions along with the copper. Since these ions are less likely to be eluted than copper ions, the potential difference can be appropriately adjusted during electrolysis to prevent the elution of these ions at the anode. Impurities inert to copper, such as gold and silver, are deposited at the bottom of the cell, and the copper plate thus produced, called electrolytic copper, is of extremely high quality and can be used to make electrical products.

The existing electrolytic copper extraction work can generate a large amount of chlorine gas to volatilize in the operation process, the chlorine gas has strong irritant odor and highly toxic gas, and the chlorine gas has suffocation property, so that the problems of environmental pollution and harm to the health of workers are caused.

Disclosure of Invention

The invention aims to provide a method for circularly regenerating acid electrolysis copper extraction without chlorine gas, which aims to solve the problems of environmental pollution and harm to the health of workers caused by volatilization of a large amount of chlorine gas generated in the operation process of the existing electrolysis copper extraction in the background technology.

In order to achieve the purpose, the invention provides the following technical scheme: a method for circularly regenerating copper by acid electrolysis without chlorine gas comprises the following steps:

step 1: carrying out electrolytic copper extraction in a chlorine-free acid electrolytic copper extraction circulating regeneration device, firstly installing a cuprous CU + ion concentration detection sensor at an anolyte outlet of a special anode plate of an integrated ionic membrane composite anode plate structure, connecting the sensor with a variable-frequency circulating pump through a controller, and adjusting the flow rate of the circulating pump according to the cuprous CU-ion concentration value detected by the anolyte outlet in real time;

step 2: when the content of cuprous (CU +) ions is less than 2g/L, the flow rate of the anolyte in the polar plate is increased, when the content of CU-10g is more than or equal to 2g/L, the content of CU-2 is more than or equal to 10g/L, the flow rate of the anolyte in the polar plate is kept unchanged, and the content of CU-10 g/L reduces the flow rate of the anolyte in the polar plate;

and step 3: a cuprous CU + ion concentration detection sensor is arranged at an anolyte inlet of a special anode plate of the integrated ionic membrane composite anode plate structure and is connected with an electrolytic copper extraction rectifier through a controller, and when the cuprous CU + ion concentration at the anode inlet is between 6 and 20g/L, the output current of the rectifier is kept at 500A;

and 4, step 4: when the concentration of cuprous CU + ions at the anode inlet is less than or equal to 5 g/h, reducing the current of the rectifier; when the concentration of cuprous CU + ions at the anode inlet is less than or equal to 2g/L, the current output current of the rectifier is adjusted to be zero, and when the concentration of cuprous CU + ions at the anode inlet is more than or equal to 20g/L, the current output current of the rectifier is increased to 700A;

and 5: collect the monovalent cuprous CU + ion concentration of anolyte entry and export of the special anode plate of integrated ionic membrane composite anode plate structure through the controller, real-time coordinated adjustment frequency conversion circulating pump and electrolysis copper extraction rectifier's flow and current size guarantee that there is certain monovalent cuprous CU + ion in the special anode plate runner of integrated ionic membrane composite anode plate structure, restrain the electrochemical reaction that positive pole district chloridion becomes chlorine.

Preferably, the chlorine-free acid electrolysis copper extraction circulating regeneration equipment comprises a working panel, a rectifier is arranged on the front end face of the working panel, one side of the rectifier is provided with a variable frequency circulating pump, an anode plate and a controller, the liquid inlet end and the liquid outlet end of the anode plate are respectively provided with an anolyte conveying pipe and an anolyte discharge pipe, one end of the anolyte delivery pipe and one end of the anolyte discharge pipe are respectively connected with the outlet and the inlet of the variable-frequency circulating pump in a sealing way, a first concentration sensor and a second concentration sensor are respectively arranged on the anolyte delivery pipe and the anolyte discharge pipe, and the first concentration sensor and the second concentration sensor are respectively arranged with the anolyte delivery pipe and the anolyte discharge pipe through flanges in a sealing way, and the outer walls of the anolyte conveying pipe and the anolyte discharge pipe are provided with pipeline pressing blocks, and a frame connecting plate is arranged below the pipeline pressing blocks.

Preferably, the upper end of anode plate is provided with the installation suspension, and installs the suspension and pass through screw and work panel fixed mounting, all be provided with the installation bedplate on the rear end face of rectifier and controller, and installation bedplate and rectifier and controller integrated into one piece set up, install the end cap bolt in the inside mounting hole of installation bedplate and work panel.

Preferably, be provided with uide bushing and screw thread plug bush on the outer wall of end cap bolt, and uide bushing and screw thread plug bush integrated into one piece set up, the one end of screw thread plug bush is provided with the expansion opening, and expands opening and screw thread plug bush integrated into one piece and set up, the inside of screw thread plug bush and uide bush is provided with drive screw, drive screw and screw thread plug bush screw thread swing joint, and drive screw and end cap bolt integrated into one piece set up.

Preferably, the one end of drive screw is provided with struts the end, and struts the end and set up with drive screw integrated into one piece, the one end of uide bushing is provided with the closed crown plate, and closed crown plate and uide bushing integrated into one piece set up, the inside bore of closed crown plate is less than the size of end cap bolt.

Preferably, the both ends of frame fishplate bar all are provided with the laminating end seat, and laminating end seat and frame fishplate bar integrated into one piece set up, install fastening bolt in the inside through-hole of laminating end seat, and laminating end seat passes through fastening bolt and working panel fixed connection, be provided with fibre cloth cover on the hookup location of pipeline briquetting and two laminating end seats, the both ends of fibre cloth cover all are provided with the connection end, and the connection end passes through screw and pipeline briquetting and laminating end seat fixed connection.

Preferably, the inner wall of the fiber cloth sleeve is provided with steel wire stays, every two adjacent steel wire stays are movably connected through a movable connecting shaft, a return spring is arranged at the center of the fiber cloth sleeve, spring connecting seats are arranged at the two ends of the return spring and are integrally formed with the return spring, and the spring connecting seats are fixedly connected with connecting ends through screws.

Preferably, the output end of the rectifier is electrically connected with the input end of the controller, and the output end of the controller is electrically connected with the input ends of the variable-frequency circulating pump, the first concentration sensor and the second concentration sensor.

Preferably, the first concentration sensor is a cuprous CU + ion concentration detection sensor, and the second concentration sensor is a cuprous CU-ion concentration detection sensor.

Preferably, the anode plate is a special anode plate with an integrated ionic membrane composite anode plate structure.

Compared with the prior art, the invention has the beneficial effects that:

1. the invention collects the concentration of cuprous CU + ions at the anolyte inlet and outlet of the special anode plate of the integrated ionic membrane composite anode plate structure through the controller, cooperatively adjusts the flow and the current of the variable frequency circulating pump and the electrolytic copper extraction rectifier in real time, ensures that certain cuprous CU + ions are arranged in the special anode plate flow passage of the integrated ionic membrane composite anode plate structure, thus, the electrochemical reaction that the chlorine ions in the anode area are changed into the chlorine gas is inhibited, the anode area is ensured not to generate the chlorine gas in the whole electrolysis process, the oxidation-reduction potential of the cuprous CU + ions to the cupric CU2+ is 519mv, the oxidation-reduction potential of the chlorine ions CL-to the chlorine gas is 1359mv, the method 1-4 ensures that certain cuprous CU + ions exist in the anode region, so that no chlorine is generated in the whole electrolysis process, and the chlorine-free acidic electrolysis copper extraction is realized.

2. A cuprous CU + ion concentration detection sensor is arranged at an anolyte inlet of a special anode plate of the integrated ionic membrane composite anode plate structure and is connected with an electrolytic copper extraction rectifier through a controller, when the cuprous CU + ion concentration at the anode inlet is between 6 and 20g/L, the output current of the rectifier is kept at 500A, and when the cuprous CU + ion concentration at the anode inlet is less than or equal to 5 g/L, the current of the rectifier is reduced; when the concentration of cuprous CU + ions at the anode inlet is less than or equal to 2g/L, the current output current of the rectifier is adjusted to zero, and when the concentration of cuprous CU + ions at the anode inlet is more than or equal to 20g/L, the current output current of the rectifier is increased to 700A, so that the function of regulating the working current by frequency conversion is achieved.

3. A cuprous CU + ion concentration detection sensor is installed at an anolyte outlet of a special anode plate of the integrated ionic membrane composite anode plate structure and is connected with a variable-frequency circulating pump through a controller, the flow rate of the circulating pump is adjusted according to the value of the cuprous CU-ion concentration detected by the anolyte outlet in real time, when the value of cuprous CU + ion is lower than 2g/L, the flow rate of anolyte in the anode plate is increased, when CU-10g is larger than or equal to L, 2 is larger than or equal to CU-10 g/L, the flow rate of anolyte in the anode plate is kept unchanged, CU-10 g/L reduces the flow rate of anolyte in the anode plate, and the purpose of controllably adjusting the flow rate is achieved.

Drawings

FIG. 1 is a schematic diagram of the overall steps of the cyclic regeneration method for chlorine-free acidic electrolytic copper extraction according to the present invention;

FIG. 2 is a schematic view of the overall structure of the chlorine-free acidic electrolysis copper extraction recycling device of the present invention;

FIG. 3 is a schematic diagram of a pipe briquette structure according to the present invention;

FIG. 4 is a schematic view of the internal structure of the fiber cloth cover of the present invention;

FIG. 5 is a schematic view of the end cap latch of the present invention;

FIG. 6 is a schematic view of the working flow of the chlorine-free acidic electrolysis copper extraction recycling device.

In the figure: 1. a working panel; 2. an anode plate; 3. mounting a suspension; 4. a rectifier; 5. mounting a seat plate; 6. a controller; 7. an end cap latch; 8. a variable frequency circulating pump; 9. an anolyte transport tube; 10. an anolyte discharge pipe; 11. a first concentration sensor; 12. a second concentration sensor; 13. pressing the pipeline into blocks; 14. frame joint plates; 15. attaching the end seat; 16. fastening a bolt; 17. a fiber cloth cover; 18. connecting the end heads; 19. a steel wire stay; 20. a movable connecting shaft; 21. a return spring; 22. a spring connecting seat; 23. a closed ring plate; 24. a guide sleeve; 25. inserting a thread; 26. a drive screw; 27. expanding the opening; 28. the end head is spread.

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.

Referring to fig. 1-6, an embodiment of the present invention is shown: a method for circularly regenerating copper by acid electrolysis without chlorine gas comprises the following steps:

step 1: carrying out electrolytic copper extraction in a chlorine-free acid electrolytic copper extraction circulating regeneration device, firstly installing a cuprous CU + ion concentration detection sensor at an anolyte outlet of a special anode plate of an integrated ionic membrane composite anode plate structure, connecting the sensor with a variable-frequency circulating pump through a controller, and adjusting the flow rate of the circulating pump according to the cuprous CU-ion concentration value detected by the anolyte outlet in real time;

step 2: when the content of cuprous (CU +) ions is less than 2g/L, the flow rate of the anolyte in the polar plate is increased, when the content of CU-10g is more than or equal to 2g/L, the content of CU-2 is more than or equal to 10g/L, the flow rate of the anolyte in the polar plate is kept unchanged, and the content of CU-10 g/L reduces the flow rate of the anolyte in the polar plate;

and step 3: a cuprous CU + ion concentration detection sensor is arranged at an anolyte inlet of a special anode plate of the integrated ionic membrane composite anode plate structure and is connected with an electrolytic copper extraction rectifier through a controller, and when the cuprous CU + ion concentration at the anode inlet is between 6 and 20g/L, the output current of the rectifier is kept at 500A;

and 4, step 4: when the concentration of cuprous CU + ions at the anode inlet is less than or equal to 5 g/h, reducing the current of the rectifier; when the concentration of cuprous CU + ions at the anode inlet is less than or equal to 2g/L, the current output current of the rectifier is adjusted to be zero, and when the concentration of cuprous CU + ions at the anode inlet is more than or equal to 20g/L, the current output current of the rectifier is increased to 700A;

and 5: collect the monovalent cuprous CU + ion concentration of anolyte entry and export of the special anode plate of integrated ionic membrane composite anode plate structure through the controller, real-time coordinated adjustment frequency conversion circulating pump and electrolysis copper extraction rectifier's flow and current size guarantee that there is certain monovalent cuprous CU + ion in the special anode plate runner of integrated ionic membrane composite anode plate structure, restrain the electrochemical reaction that positive pole district chloridion becomes chlorine.

Furthermore, the chlorine-free acid electrolysis copper extraction circulation regeneration equipment comprises a working panel 1, a rectifier 4 is arranged on the front end face of the working panel 1, a variable frequency circulating pump 8, an anode plate 2 and a controller 6 are arranged on one side of the rectifier 4, an anolyte conveying pipe 9 and an anolyte discharge pipe 10 are respectively arranged on the liquid inlet end and the liquid outlet end of the anode plate 2, one end of the anolyte conveying pipe 9 and one end of the anolyte discharge pipe 10 are respectively connected with the outlet and the inlet of the variable frequency circulating pump 8 in a sealing way, a first concentration sensor 11 and a second concentration sensor 12 are respectively arranged on the anolyte conveying pipe 9 and the anolyte discharge pipe 10, and the first concentration sensor 11 and the second concentration sensor 12 are respectively installed with the anolyte conveying pipe 9 and the anolyte discharge pipe 10 through flanges in a sealing manner, the outer walls of the anolyte conveying pipe 9 and the anolyte discharge pipe 10 are provided with pipeline pressing blocks 13, and a frame connecting plate 14 is arranged below the pipeline pressing blocks 13.

Further, the upper end of anode plate 2 is provided with installation suspension 3, and installation suspension 3 passes through screw and 1 fixed mounting of work panel, all is provided with installation bedplate 5 on the rear end face of rectifier 4 and controller 6, and installation bedplate 5 sets up with rectifier 4 and controller 6 integrated into one piece, installs end cap bolt 7 in the inside mounting hole of installation bedplate 5 and work panel 1.

Further, be provided with uide bushing 24 and screw thread plug bush 25 on the outer wall of end cap bolt 7, and uide bushing 24 and screw thread plug bush 25 integrated into one piece set up, the one end of screw thread plug bush 25 is provided with expansion opening 27, and expansion opening 27 sets up with screw thread plug bush 25 integrated into one piece, the inside of screw thread plug bush 25 and uide bushing 24 is provided with drive screw 26, drive screw 26 and screw thread plug bush 25 screw thread swing joint, and drive screw 26 sets up with end cap bolt 7 integrated into one piece.

Further, one end of the drive screw 26 is provided with a distraction end 28, the distraction end 28 and the drive screw 26 are integrally formed, one end of the guide sleeve 24 is provided with a closed ring plate 23, the closed ring plate 23 and the guide sleeve 24 are integrally formed, and the inner caliber of the closed ring plate 23 is smaller than the size of the end cap bolt 7.

Further, the both ends of frame fishplate bar 14 all are provided with laminating end seat 15, and laminating end seat 15 sets up with 14 integrated into one piece of frame fishplate bar, install fastening bolt 16 in the inside through-hole of laminating end seat 15, and laminating end seat 15 passes through fastening bolt 16 and working panel 1 fixed connection, be provided with fibre cloth cover 17 on the hookup location of pipeline briquetting 13 and two laminating end seats 15, the both ends of fibre cloth cover 17 all are provided with connection end 18, and connect end 18 through screw and pipeline briquetting 13 and laminating end seat 15 fixed connection.

Further, be provided with steel wire stay 19 on the inner wall of fibre cloth cover 17, through activity spiale 20 swing joint between two adjacent steel wire stays 19, be provided with return spring 21 on the central point of fibre cloth cover 17 puts, and return spring 21's both ends all are provided with spring connecting seat 22, and spring connecting seat 22 and return spring 21 integrated into one piece set up, and spring connecting seat 22 passes through screw and connection end 18 fixed connection.

Further, the output end of the rectifier 4 is electrically connected with the input end of the controller 6, and the output end of the controller 6 is electrically connected with the input ends of the variable frequency circulating pump 8, the first concentration sensor 11 and the second concentration sensor 12.

Further, the first concentration sensor 11 is a cuprous CU + ion concentration detection sensor, and the second concentration sensor 12 is a cuprous CU-ion concentration detection sensor.

Further, the anode plate 2 is a special anode plate with an integrated ionic membrane composite anode plate structure.

It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.