A copper and manganese co-extraction process for comprehensive wet recovery

Abstract

The present invention relates to the field of hydrometallurgical technology, discloses a copper-manganese co-extraction process for wet comprehensive recovery, comprising the following steps: S1, adding acid solution to be recovered after pulverizing the electronic components to be recovered, passing SO2 treatment after heating, and obtaining leachate; S2, passing the leachate into a multi-stage countercurrent extraction system for extraction; S3, the extraction phase is stripped by sulfuric acid after outflowing from the light phase outlet of the multi-stage countercurrent extraction system to obtain a mixed solution; S4, adding reduced iron powder to the mixed solution for reaction, filtering and washing the post-reaction solution, the filter residue is active copper powder, and the filtrate is a manganese-containing solution to complete the separation of copper and manganese. The composite extractant of the present invention is more excellent than a single extractant in extracting and separating manganese and copper in cobalt leachate, and the co-extractant strengthens the extraction effect, and 3,5-diisooctyl pyridinedicarboxylate can improve the stripping efficiency without affecting the extraction efficiency, thereby increasing the net transfer amount of copper and facilitating the separation of copper and manganese after extraction.

Description

Technical Field

[0001] The invention belongs to the technical field of hydrometallurgy, and in particular relates to a copper-manganese co-extraction process for comprehensive wet recovery. Background Art

[0002] With the rapid development of information and communications technology, the replacement cycle of electronic and electrical products has shortened, and a large number of electronic and electrical products are eliminated every year. Waste electronic products mainly consist of three major components: the body, battery, and motherboard. Batteries and motherboards contain a variety of metals with recycling value, representing high-quality "urban mineral" resources. These recyclable metals can be simply divided into two categories: common metals such as Cu, Fe, Al, Mn, Zn, Sn, and Ni, and precious metals such as Ag, Au, and Pa. Currently, many research and development institutions and enterprises are recycling the metals in waste electronic products, using methods such as pyrometallurgy, physical-mechanical methods, and hydrometallurgy.

[0003] Pyrometallurgy suffers from the drawbacks of large equipment investments, severe air pollution, and high exhaust gas treatment costs. Physical and mechanical methods can only produce metal-enriched aggregates and require a certain degree of metal dissociation within the circuit board for effective separation. Hydrometallurgy has been extensively studied, with most approaches using various chemical reagents to dissolve the metal components in the sample into a solution for separation. Extraction techniques are often used in hydrometallurgy to remove impurities from leachates. However, during the extraction process with organic extractants, such as P2O4, copper and manganese are difficult to separate and are subsequently introduced into the stripping acid. When the copper content is not high, the addition of soda ash to this mixed solution precipitates all the valuable metals, including copper and manganese. However, when the copper content in this solution is relatively high, the subsequent separation of copper and manganese becomes significantly more difficult using these methods. Summary of the Invention

[0004] In order to solve the deficiencies mentioned in the above-mentioned background technology, the object of the present invention is to provide a copper-manganese co-extraction process for wet comprehensive recovery. The composite extractant has better performance than a single extractant in extracting and separating manganese and copper from cobalt leachate. The co-extractant enhances the extraction effect. 3,5-diisooctyl pyridinedicarboxylate can improve the back-extraction efficiency without affecting the extraction efficiency, thereby increasing the net transfer of copper and facilitating the separation of copper and manganese after extraction. At the same time, a multi-stage countercurrent extraction system is used to extract the leachate. The leachate is extracted multiple times, and the heavy phase and the light phase can be fully mixed through the reflux mixing tube, which can further improve the extraction rate of copper and manganese ions.

[0005] The purpose of the present invention can be achieved through the following technical solutions:

[0006] The present invention provides a copper and manganese co-extraction process for wet comprehensive recovery, comprising the following steps:

[0007] S1. Crush the electronic components to be recycled and add them to the acid solution. Stir and mix them evenly, then heat to 70-90°C. Add SO2 at a rate of 0.1-0.5 L / min for 3-5 hours to obtain a leachate.

[0008] S2. The leachate is passed through the heavy phase inlet of the multi-stage countercurrent extraction system, and the extract is passed through the light phase inlet of the multi-stage countercurrent extraction system, and extracted at 20-25°C for 20-30 minutes;

[0009] S3, the raffinate phase flows out from the heavy phase outlet of the multi-stage countercurrent extraction system for subsequent metal ion separation process, and the extract phase flows out from the light phase outlet of the multi-stage countercurrent extraction system and is stripped by sulfuric acid to obtain a mixed solution of copper sulfate and manganese sulfate;

[0010] S4. Add reduced iron powder to the mixed solution of copper sulfate and manganese sulfate, react for 20-40 minutes, filter and wash the solution after the reaction, the filter residue is active copper powder, and the filtrate is a manganese-containing solution, thereby completing the separation of copper and manganese.

[0011] Preferably, the acid solution in step S1 is a mixture of sulfuric acid and hydrogen peroxide, and the solid-liquid ratio of the electronic components to be recovered to the acid solution is 30-50 g / L.

[0012] Preferably, in step S2, the flow ratio of the leachate to the extract is 1:1-3.

[0013] Preferably, the extract comprises 30-50 parts of an extractant, 10-20 parts of a co-extractant, and 100-150 parts of a diluent, wherein the extractant is a mixture of di-(2-ethylhexyl) phosphate and 2-ethylhexyl phosphate 2-ethylhexyl ester in a mass ratio of 3-5:1, the co-extractant is a mixture of tributyl phosphate and diisooctyl 3,5-pyridinedicarboxylate in a mass ratio of 1-2:1, and the diluent is sulfonated kerosene.

[0014] Preferably, the structural formula of diisooctyl 3,5-pyridinedicarboxylate is as follows:

[0015] ;

[0016] The preparation method of the diisooctyl 3,5-pyridinedicarboxylate comprises the following steps:

[0017] A. Dissolve potassium permanganate and tetrabutylammonium bromide in water, then add the solution into a reflux reactor and heat to 45-50°C;

[0018] B. Slowly add 3,5-lutidine dropwise to the reaction system and reflux for 1-3 hours. After the purple color of the reaction system disappears, stop heating and cool to room temperature. Filter under reduced pressure and wash with deionized water. Collect the filtrate and washing solution.

[0019] C. Heat the filtrate and washing solution and concentrate them 3-5 times. Add concentrated hydrochloric acid while stirring the concentrate until the pH of the concentrate is 1-2. After standing for 1-2 hours, filter under reduced pressure and wash with deionized water. Collect the filter residue and dry it in a constant temperature drying oven to obtain 3,5-pyridinedicarboxylic acid.

[0020] D. Dissolve 3,5-pyridinedicarboxylic acid and thionyl chloride in carbon tetrachloride, heat to 60-70° C., then add isooctyl alcohol to the mixed solution of 3,5-pyridinedicarboxylic acid and thionyl chloride, react for 1-3 hours, and evaporate to remove excess solvent to obtain the diisooctyl 3,5-pyridinedicarboxylate.

[0021] Preferably, in step S4, the copper content in the solution is first determined, and reduced iron powder is added in a mass ratio of 1:1 according to the copper content.

[0022] Preferably, the multi-stage countercurrent extraction system is composed of multiple centrifugal extraction towers in series, the centrifugal extraction tower including a tower body, the outer wall of the tower body is fixedly installed on the support frame, the bottom of the support frame is fixedly connected to the base, a partition is provided on the lower side of the interior of the tower body, the partition divides the tower body into a centrifugal separation chamber and a two-phase mixing chamber, a drive shaft is provided between the centrifugal separation chamber and the two-phase mixing chamber, a feed hole is provided in the middle of the partition, a reflux mixing pipe is fixedly installed inside the two-phase mixing chamber, a heavy phase inlet and a light phase inlet are fixedly provided on the outer walls of the tower body on both sides of the two-phase mixing chamber, the heavy phase inlet and the light phase inlet are both deviated from the center of the tower body, the heavy phase inlet and the light phase inlet are symmetrical around the center of the tower body, a heavy phase collecting chamber and a light phase collecting chamber are provided on the outer wall of the tower body on the upper side of the centrifugal separation chamber, the heavy phase collecting chamber is arranged above the light phase collecting chamber, a sealing cover plate is fixedly installed on the top of the tower body, the upper end of the drive shaft is rotatably connected to the sealing cover plate, the top end of the drive shaft is fixedly connected to the output shaft of the motor, and the motor is fixedly installed on the top of the sealing cover plate.

[0023] Preferably, a drum is fixedly mounted on the surface of the drive shaft inside the centrifugal separation chamber, a baffle is fixedly mounted on the surface of the drive shaft above the feed hole, an annular guide plate is fixedly mounted on the inner wall of the tower body above the baffle, and several strip plates are fixedly mounted on the bottom of the annular guide plate, and the strip plates are arranged in an annular array.

[0024] Preferably, a first discharge hole is provided on the inner wall of the tower body corresponding to the light phase collection chamber, a light phase outlet is provided on the outer wall of the tower body corresponding to the light phase collection chamber, a first weir plate is fixedly installed on the inner wall of the tower body below the first discharge hole, a second discharge hole is provided on the inner wall of the tower body corresponding to the heavy phase collection chamber, the first discharge hole and the second discharge hole are respectively located on both sides of the tower body, a heavy phase outlet is provided on the outer wall of the tower body corresponding to the heavy phase collection chamber, a second weir plate is fixedly installed on the inner wall of the tower body below the second discharge hole, and a baffle is fixedly installed on the inner wall of the tower body between the first weir plate and the second weir plate, and the cross-section of the baffle is L-shaped.

[0025] Preferably, the reflux mixing tube includes a first tube body, a spoiler and a second tube body, the first tube body, the spoiler and the second tube body are coaxially arranged, the first tube body is fixedly connected to the bottom of the partition, and the second tube body is fixedly connected to the bottom of the tower body. The spoiler includes an annular seat, and the upper and lower sides of the annular seat are rotatably connected to the first tube body and the second tube body respectively. At the same time, the inner and outer diameters of the annular seat are the same as those of the first tube body and the second tube body. A number of first spoiler blades are fixedly installed on the inner wall of the annular seat, and the middle of the first spoiler blade is fixedly connected to the drive shaft. A number of second spoiler blades are fixedly installed on the outer wall of the annular seat, and the first spoiler blades and the second spoiler blades are arranged in an annular array. A number of reflux holes are opened at the lower end of the second tube body.

[0026] Beneficial effects of the present invention:

[0027] The present invention utilizes a combination of di-(2-ethylhexyl) phosphate (P204) and 2-ethylhexyl phosphate (P507) as extractants, resulting in superior performance in extracting and separating manganese and copper from cobalt leachate compared to single extractants. Furthermore, the present invention utilizes a combination of tributyl phosphate (TBP) and diisooctyl 3,5-pyridinedicarboxylate as synergistic extractants. These synergistic extractants do not directly coordinate metal ions but instead hydrogen-bond with organic ligands in the extractant, increasing the extractant's hydrophobicity and significantly improving the distribution ratio. During the synergistic extraction process, the extractants displace water molecules in the extractant, forming a highly hydrophobic extractant and enhancing the extraction effect. Diisooctyl 3,5-pyridinedicarboxylate improves back-extraction efficiency without compromising extraction efficiency, thereby increasing the net transfer of copper and facilitating the separation of copper and manganese after extraction.

[0028] In addition, the present invention adopts a multi-stage countercurrent extraction system to extract the leachate, the heavy phase flows out of the first-stage centrifugal extraction tower and then flows into the second-stage centrifugal extraction tower, the heavy phase flowing out of the second-stage centrifugal extraction tower flows into the third-stage centrifugal extraction tower, and the light phase is the opposite, first passing through the third-stage centrifugal extraction tower and mixing with the heavy phase therein and then centrifugally separated, and then flowing out and flowing into the second-stage centrifugal extraction tower, the light phase flowing out of the second-stage centrifugal extraction tower flows into the first-stage centrifugal extraction tower. In this way, the leachate is extracted multiple times, and the heavy phase and the light phase of the centrifugal extraction tower of the present invention can be fully mixed through the reflux mixing tube, which can further improve the extraction rate of copper and manganese ions therein. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The present invention will be further described below with reference to the accompanying drawings.

[0030] Figure 1 Schematic diagram of the overall structure of the multi-stage countercurrent extraction system of the present invention;

[0031] Figure 2 Schematic diagram of the internal structure of the centrifugal extraction tower of the present invention;

[0032] Figure 3 It is a schematic cross-sectional view of the guide plate of the centrifugal extraction tower of the present invention;

[0033] Figure 4 It is a structural schematic diagram of the reflux mixing tube of the centrifugal extraction tower of the present invention.

[0034] In the figure: 1-tower body, 101-centrifugal separation chamber, 102-two-phase mixing chamber, 103-heavy phase collecting chamber, 104-light phase collecting chamber, 105-first discharge hole, 106-second discharge hole, 2-support frame, 3-base, 4-partition, 401-feed hole, 5-drive shaft, 6-mixing tube, 7-heavy phase inlet, 8-light phase inlet, 9-sealing cover, 10-motor, 11-drum, 12-baffle, 13-annular guide plate, 14-strip plate, 15-light phase outlet, 16-first weir, 17-heavy phase outlet, 18-second weir, 19-baffle, 20-first tube body, 21-spoiler, 22-second tube body, 23-annular seat, 24-first spoiler blade, 25-second spoiler blade. DETAILED DESCRIPTION

[0035] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0036] Example 1

[0037] A copper-manganese co-extraction process for comprehensive wet recovery comprises the following steps:

[0038] S1. The electronic components to be recycled are crushed and added to a mixture of sulfuric acid and hydrogen peroxide at a solid-liquid ratio of 30 g / L. After stirring and mixing evenly, the mixture is heated to 90°C and SO2 is introduced at a rate of 0.1 L / min for 5 hours to obtain a leachate.

[0039] S2, the leachate is passed into the heavy phase inlet of the multi-stage countercurrent extraction system, and the extract is passed into the light phase inlet of the multi-stage countercurrent extraction system, the flow ratio of the leachate to the extract is controlled to be 1:1, and the extraction is carried out at 25°C for 20 minutes;

[0040] S3, the raffinate phase flows out from the heavy phase outlet of the multi-stage countercurrent extraction system for subsequent metal ion separation process, and the extract phase flows out from the light phase outlet of the multi-stage countercurrent extraction system and is stripped by sulfuric acid to obtain a mixed solution of copper sulfate and manganese sulfate;

[0041] S4. Determine the copper content in the mixed solution, add reduced iron powder in a mass ratio of 1:1 to the mixed solution according to the copper content, react for 20 minutes, filter and wash the solution after the reaction, the filter residue is active copper powder, and the filtrate is a manganese-containing solution, thereby completing the separation of copper and manganese.

[0042] The extract includes 50 parts of an extractant, 10 parts of a co-extractant, and 150 parts of a diluent. The extractant is a mixture of di-(2-ethylhexyl) phosphate and 2-ethylhexyl phosphate 2-ethylhexyl ester in a mass ratio of 1:1, the co-extractant is a mixture of tributyl phosphate and diisooctyl 3,5-pyridinedicarboxylate in a mass ratio of 1:1, and the diluent is sulfonated kerosene.

[0043] The preparation method of diisooctyl 3,5-pyridinedicarboxylate comprises the following steps:

[0044] A. Dissolve potassium permanganate and tetrabutylammonium bromide in water, then add the solution into a reflux reactor and heat to 45°C;

[0045] B. Slowly add 3,5-lutidine dropwise to the above reaction system and reflux for 3 hours. After the purple color of the reaction system disappears, stop heating and cool to room temperature. Filter under reduced pressure and wash with deionized water. Collect the filtrate and washing liquid.

[0046] C. The filtrate and washing solution were concentrated by heating for 3 times, and concentrated hydrochloric acid was added to the concentrate while stirring until the pH of the concentrate reached 2. After standing for 1 hour, the concentrate was filtered under reduced pressure and washed with deionized water. The filter residue was collected and placed in a constant temperature drying oven to dry to obtain 3,5-pyridinedicarboxylic acid;

[0047] D. Dissolve 3,5-pyridinedicarboxylic acid and thionyl chloride in carbon tetrachloride, heat to 70° C., then add isooctyl alcohol to the mixed solution of 3,5-pyridinedicarboxylic acid and thionyl chloride, react for 1 hour, and evaporate to remove excess solvent to obtain the diisooctyl 3,5-pyridinedicarboxylate.

[0048] Example 2

[0049] A copper-manganese co-extraction process for comprehensive wet recovery comprises the following steps:

[0050] S1. The electronic components to be recycled are crushed and added to a mixture of sulfuric acid and hydrogen peroxide at a solid-liquid ratio of 50 g / L. After stirring and mixing, the mixture is heated to 70°C and SO2 is introduced at a rate of 0.5 L / min for 3 hours to obtain a leachate.

[0051] S2, the leachate is passed into the heavy phase inlet of the multi-stage countercurrent extraction system, and the extract is passed into the light phase inlet of the multi-stage countercurrent extraction system, the flow ratio of the leachate to the extract is controlled to be 1:3, and the extraction is carried out at 20°C for 30 minutes;

[0052] S3, the raffinate phase flows out from the heavy phase outlet of the multi-stage countercurrent extraction system for subsequent metal ion separation process, and the extract phase flows out from the light phase outlet of the multi-stage countercurrent extraction system and is stripped by sulfuric acid to obtain a mixed solution of copper sulfate and manganese sulfate;

[0053] S4. Determine the copper content in the mixed solution, add reduced iron powder in a mass ratio of 1:1 to the mixed solution according to the copper content, react for 20 minutes, filter and wash the solution after the reaction, the filter residue is active copper powder, and the filtrate is a manganese-containing solution, thereby completing the separation of copper and manganese.

[0054] The extract includes 30 parts of an extractant, 20 parts of a co-extractant, and 100 parts of a diluent. The extractant is a mixture of di-(2-ethylhexyl) phosphate and 2-ethylhexyl phosphate 2-ethylhexyl ester in a mass ratio of 1:1, the co-extractant is a mixture of tributyl phosphate and diisooctyl 3,5-pyridinedicarboxylate in a mass ratio of 2:1, and the diluent is sulfonated kerosene.

[0055] The preparation method of diisooctyl 3,5-pyridinedicarboxylate comprises the following steps:

[0056] A. Dissolve potassium permanganate and tetrabutylammonium bromide in water, then add the solution into a reflux reactor and heat to 45°C;

[0057] B. Slowly add 3,5-lutidine dropwise to the above reaction system and reflux for 3 hours. After the purple color of the reaction system disappears, stop heating and cool to room temperature. Filter under reduced pressure and wash with deionized water. Collect the filtrate and washing liquid.

[0058] C. The filtrate and washing solution were concentrated by heating for 5 times, and concentrated hydrochloric acid was added to the concentrate while stirring until the pH of the concentrate was 1. After standing for 2 hours, the concentrate was filtered under reduced pressure and washed with deionized water. The filter residue was collected and placed in a constant temperature drying oven to dry to obtain 3,5-pyridinedicarboxylic acid;

[0059] D. Dissolve 3,5-pyridinedicarboxylic acid and thionyl chloride in carbon tetrachloride, heat to 60° C., then add isooctyl alcohol to the mixed solution of 3,5-pyridinedicarboxylic acid and thionyl chloride, react for 3 hours, and evaporate to remove excess solvent to obtain the diisooctyl 3,5-pyridinedicarboxylate.

[0060] Example 3

[0061] A copper-manganese co-extraction process for comprehensive wet recovery comprises the following steps:

[0062] S1. The electronic components to be recycled are crushed and added to a mixture of sulfuric acid and hydrogen peroxide at a solid-liquid ratio of 40 g / L. After stirring and mixing, the mixture is heated to 80°C and SO2 is introduced at a rate of 0.3 L / min for 4 hours to obtain a leachate.

[0063] S2, the leachate is passed into the heavy phase inlet of the multi-stage countercurrent extraction system, and the extract is passed into the light phase inlet of the multi-stage countercurrent extraction system, the flow ratio of the leachate to the extract is controlled to be 1:2, and the extraction is carried out at 22°C for 25 minutes;

[0064] S3, the raffinate phase flows out from the heavy phase outlet of the multi-stage countercurrent extraction system for subsequent metal ion separation process, and the extract phase flows out from the light phase outlet of the multi-stage countercurrent extraction system and is stripped by sulfuric acid to obtain a mixed solution of copper sulfate and manganese sulfate;

[0065] S4. Determine the copper content in the mixed solution, add reduced iron powder in a mass ratio of 1:1 to the mixed solution according to the copper content, react for 30 minutes, filter and wash the solution after the reaction, the filter residue is active copper powder, and the filtrate is a manganese-containing solution, thereby completing the separation of copper and manganese.

[0066] The extract includes 40 parts of an extractant, 15 parts of a co-extractant, and 125 parts of a diluent. The extractant is a mixture of di-(2-ethylhexyl) phosphate and 2-ethylhexyl phosphate 2-ethylhexyl ester in a mass ratio of 1:1, the co-extractant is a mixture of tributyl phosphate and diisooctyl 3,5-pyridinedicarboxylate in a mass ratio of 1:1, and the diluent is sulfonated kerosene.

[0067] The preparation method of diisooctyl 3,5-pyridinedicarboxylate comprises the following steps:

[0068] A. Dissolve potassium permanganate and tetrabutylammonium bromide in water, then add the solution into a reflux reactor and heat to 48°C;

[0069] B. Slowly add 3,5-lutidine dropwise to the above reaction system and reflux for 2 h. After the purple color of the reaction system disappears, stop heating and cool to room temperature. Filter under reduced pressure and wash with deionized water. Collect the filtrate and washing liquid.

[0070] C. The filtrate and washing solution were concentrated by heating to 4 times, and concentrated hydrochloric acid was added to the concentrate while stirring until the pH of the concentrate was 1. After standing for 1.5 hours, the concentrate was filtered under reduced pressure and washed with deionized water. The filter residue was collected and placed in a constant temperature drying oven to dry to obtain 3,5-pyridinedicarboxylic acid;

[0071] D. Dissolve 3,5-pyridinedicarboxylic acid and thionyl chloride in carbon tetrachloride, heat to 65° C., then add isooctyl alcohol to the mixed solution of 3,5-pyridinedicarboxylic acid and thionyl chloride, react for 2 hours, and evaporate to remove excess solvent to obtain the diisooctyl 3,5-pyridinedicarboxylate.

[0072] A multi-stage countercurrent extraction system is composed of multiple centrifugal extraction towers connected in series. The centrifugal extraction tower includes a tower body 1. The outer wall of the tower body 1 is fixedly mounted on a support frame 2. The bottom of the support frame 2 is fixedly connected to a base 3. A partition 4 is provided on the lower side of the interior of the tower body 1. The partition 4 divides the tower body 1 into a centrifugal separation chamber 101 and a two-phase mixing chamber 102. A drive shaft 5 is provided between the centrifugal separation chamber 101 and the two-phase mixing chamber 102. A feed hole 401 is provided in the middle of the partition 4. A reflux mixing tube 6 is fixedly installed inside the two-phase mixing chamber 102. A heavy phase inlet 7 and a light phase inlet 8 are fixedly provided on the outer walls of the tower body 1 on both sides of the two-phase mixing chamber 102. The heavy phase inlet 7 and the light phase inlet 8 are both deviated from the center of the tower body 1. The heavy phase inlet 7 and the light phase inlet 8 are symmetrical around the center of the tower body 1. The outer wall of the tower body 1 on the upper side of the centrifugal separation chamber 101 is provided with a heavy phase collection chamber 103 and a light phase collection chamber 104. The heavy phase collection chamber 103 is arranged above the light phase collection chamber 104. A sealing cover plate 9 is fixedly installed on the top of the tower body 1. The upper end of the drive shaft 5 is rotatably connected to the sealing cover plate 9. The top end of the drive shaft 5 is fixedly connected to the output shaft of the motor 10. The motor 10 is fixedly installed on the top of the sealing cover plate 9. During extraction, the leachate and the extract enter the two-phase mixing chamber 102 of the tower body 1 from the heavy phase inlet 7 and the light phase inlet 8 respectively. The leachate and the extract are fully mixed through the reflux mixing tube 6, so that the Cu in the leachate is extracted by the extractant. 2+ and Mn 2+ Extracted.

[0073] A drum 11 is fixedly mounted on the surface of the drive shaft 5 inside the centrifugal separation chamber 101, a baffle 12 is fixedly mounted on the surface of the drive shaft 5 above the feed hole 401, an annular guide plate 13 is fixedly mounted on the inner wall of the tower body 1 above the baffle 12, and a plurality of strip plates 14 are fixedly mounted on the bottom of the annular guide plate 13. The strip plates 14 are arranged in an annular array. The drive shaft 5 drives the drum 11 to rotate, causing the mixed phase in the centrifugal separation chamber 101 to rotate at high speed. Under the action of centrifugal force, the light phase is enriched in the inner circle and the heavy phase is enriched in the outer circle.

[0074] The inner wall of the tower body 1 is provided with a first discharge hole 105 corresponding to the light phase collecting chamber 104, and the outer wall of the tower body 1 is provided with a light phase outlet 15 corresponding to the light phase collecting chamber 104. A first weir plate 16 is fixedly installed on the inner wall of the tower body 1 at the lower end of the first discharge hole 105, and a second discharge hole 106 is provided on the inner wall of the tower body 1 corresponding to the heavy phase collecting chamber 103. The first discharge hole 105 and the second discharge hole 106 are respectively located on both sides of the tower body 1, and a heavy phase outlet 17 is provided on the outer wall of the tower body 1 corresponding to the heavy phase collecting chamber 103. A second weir plate 18 is fixedly installed on the inner wall of the tower body 1 at the lower end of the hole 106, and a baffle plate 19 is fixedly installed on the inner wall of the tower body 1 between the first weir plate 16 and the second weir plate 18. The cross-section of the baffle plate 19 is L-shaped. The ends of the first weir plate 16 and the second weir plate 18 away from the inner wall of the tower body 1 are respectively placed in the position of the separated light phase and heavy phase, thereby guiding the light phase to flow into the light phase collecting chamber 104 and the heavy phase to flow into the heavy phase collecting chamber 103. The baffle plate 19 between the first weir plate 16 and the second weir plate 18 serves to separate the light phase and the heavy phase.

[0075] The reflux mixing tube 6 includes a first tube body 20, a spoiler 21 and a second tube body 22. The first tube body 20, the spoiler 21 and the second tube body 22 are coaxially arranged. The first tube body 20 is fixedly connected to the bottom of the partition 4, and the second tube body 22 is fixedly connected to the bottom of the tower body 1. The spoiler 21 includes an annular seat 23. The upper and lower sides of the annular seat 23 are respectively rotatably connected to the first tube body 20 and the second tube body 22. At the same time, the annular seat 23 has the same inner and outer diameters as the first tube body 20 and the second tube body 22. A number of first spoiler blades 24 are fixedly installed on the inner wall of the annular seat 23. The middle of the first spoiler blade 24 is fixedly connected to the drive shaft 5, and a number of second spoiler blades are fixedly installed on the outer wall of the annular seat 23 25, the first spoiler blades 24 and the second spoiler blades 25 are arranged in a ring array, and a plurality of reflux holes 26 are opened at the lower end of the second tube body 22. The driving shaft 5 drives the spoiler 21 to rotate, so that the light phase and the heavy phase in the space between the reflux mixing tube 6 and the inner wall of the tower body 1 flow downward under the action of the second spoiler blades 25, and then enter the reflux mixing tube 6 through the reflux holes 26. After entering the reflux mixing tube 6, the heavy phase and the light phase flow upward under the action of the first spoiler blades 24, thereby passing through the feed hole 401 and entering the centrifugal separation chamber 101. While flowing, the heavy phase and the light phase are also mixed with each other as the first spoiler blades 24 and the second spoiler blades 25 rotate.

[0076] Throughout this specification, references to terms such as "one embodiment," "example," or "specific example" indicate that the specific features, structures, materials, or characteristics described in conjunction with that embodiment or example are included in at least one embodiment or example of the present invention. In this specification, schematic representations of these terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

[0077] The basic principles, main features, and advantages of the present invention are shown and described above. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The above embodiments and descriptions are merely illustrative of the principles of the present invention. Various changes and modifications may be made to the present invention without departing from the spirit and scope of the present invention, and such changes and modifications fall within the scope of the invention as claimed.

Claims

1. A copper and manganese co-extraction process for comprehensive wet recovery, characterized in that: The following steps are involved: S1. Crush the electronic components to be recycled and add them to the acid solution. Stir and mix them evenly, then heat to 70-90°C. Add SO2 at a rate of 0.1-0.5 L / min and treat for 3-5 hours to obtain a leachate. S2. The leachate is passed through the heavy phase inlet of the multi-stage countercurrent extraction system, and the extract is passed through the light phase inlet of the multi-stage countercurrent extraction system, and extracted at 20-25°C for 20-30 minutes; S3, the raffinate phase flows out from the heavy phase outlet of the multi-stage countercurrent extraction system for subsequent metal ion separation process, and the extract phase flows out from the light phase outlet of the multi-stage countercurrent extraction system and is stripped by sulfuric acid to obtain a mixed solution of copper sulfate and manganese sulfate; S4, adding reduced iron powder to the mixed solution of copper sulfate and manganese sulfate, reacting for 20-40 minutes, filtering and washing the solution after the reaction, the filter residue is active copper powder, and the filtrate is a manganese-containing solution, completing the separation of copper and manganese; The extract comprises 30-50 parts of an extractant, 10-20 parts of a co-extractant, and 100-150 parts of a diluent. The extractant is a mixture of di-(2-ethylhexyl) phosphate and 2-ethylhexyl phosphate 2-ethylhexyl ester in a mass ratio of 3-5:

1. The co-extractant is a mixture of tributyl phosphate and diisooctyl 3,5-pyridinedicarboxylate in a mass ratio of 1-2:

1. The diluent is sulfonated kerosene.

2. The copper-manganese co-extraction process for wet comprehensive recovery according to claim 1, characterized in that: The acid solution in step S1 is a mixture of sulfuric acid and hydrogen peroxide, and the solid-to-liquid ratio of the electronic components to be recovered to the acid solution is 30-50 g / L.

3. The copper-manganese co-extraction process for wet comprehensive recovery according to claim 1, characterized in that: In step S2, the flow ratio of the leachate to the extract is 1:1-3.

4. The copper-manganese co-extraction process for wet comprehensive recovery according to claim 1, characterized in that: The structural formula of the diisooctyl 3,5-pyridinedicarboxylate is as follows: ； The preparation method of the diisooctyl 3,5-pyridinedicarboxylate comprises the following steps: A. Dissolve potassium permanganate and tetrabutylammonium bromide in water, then add the solution into a reflux reactor and heat to 45-50°C; B. Slowly add 3,5-lutidine dropwise to the reaction system and reflux for 1-3 hours. After the purple color of the reaction system disappears, stop heating and cool to room temperature. Filter under reduced pressure and wash with deionized water. Collect the filtrate and washing solution. C. Heat the filtrate and washing solution and concentrate them 3-5 times. Add concentrated hydrochloric acid while stirring the concentrate until the pH of the concentrate is 1-2. After standing for 1-2 hours, filter under reduced pressure and wash with deionized water. Collect the filter residue and dry it in a constant temperature drying oven to obtain 3,5-pyridinedicarboxylic acid. D. Dissolve 3,5-pyridinedicarboxylic acid and thionyl chloride in carbon tetrachloride, heat to 60-70° C., then add isooctyl alcohol to the mixed solution of 3,5-pyridinedicarboxylic acid and thionyl chloride, react for 1-3 hours, and evaporate to remove excess solvent to obtain the diisooctyl 3,5-pyridinedicarboxylate.

5. The copper-manganese co-extraction process for wet comprehensive recovery according to claim 1, characterized in that: The multi-stage countercurrent extraction system is composed of a plurality of centrifugal extraction towers connected in series. The centrifugal extraction tower comprises a tower body (1), the outer wall of the tower body (1) is fixedly mounted on a support frame (2), the bottom of the support frame (2) is fixedly connected to a base (3), a partition (4) is provided on the lower side of the interior of the tower body (1), the partition (4) divides the tower body (1) into a centrifugal separation chamber (101) and a two-phase mixing chamber (102), a driving shaft (5) is provided through the middle of the centrifugal separation chamber (101) and the two-phase mixing chamber (102), a feed hole (401) is provided in the middle of the partition (4), a reflux mixing tube (6) is fixedly mounted inside the two-phase mixing chamber (102), and the outer walls of the tower body (1) on both sides of the two-phase mixing chamber (102) are respectively fixed. A heavy phase inlet (7) and a light phase inlet (8) are fixedly provided, and both the heavy phase inlet (7) and the light phase inlet (8) are deviated from the center of the tower body (1). The heavy phase inlet (7) and the light phase inlet (8) are symmetrical around the center of the tower body (1). A heavy phase collecting chamber (103) and a light phase collecting chamber (104) are provided on the outer wall of the tower body (1) above the centrifugal separation chamber (101). The heavy phase collecting chamber (103) is arranged above the light phase collecting chamber (104). A sealing cover plate (9) is fixedly installed on the top of the tower body (1). The upper end of the drive shaft (5) is rotatably connected to the sealing cover plate (9). The top end of the drive shaft (5) is fixedly connected to the output shaft of the motor (10). The motor (10) is fixedly installed on the top of the sealing cover plate (9).

6. The copper-manganese co-extraction process for wet comprehensive recovery according to claim 5, characterized in that: A rotating drum (11) is fixedly mounted on the surface of the driving shaft (5) inside the centrifugal separation chamber (101), a baffle (12) is fixedly mounted on the surface of the driving shaft (5) above the feed hole (401), an annular guide plate (13) is fixedly mounted on the inner wall of the tower body (1) above the baffle (12), and a plurality of strip plates (14) are fixedly mounted on the bottom of the annular guide plate (13), wherein the strip plates (14) are arranged in an annular array.

7. The copper-manganese co-extraction process for wet comprehensive recovery according to claim 5, characterized in that: A first discharge hole (105) is provided on the inner wall of the tower body (1) corresponding to the light phase collection chamber (104), a light phase outlet (15) is provided on the outer wall of the tower body (1) corresponding to the light phase collection chamber (104), a first weir plate (16) is fixedly installed on the inner wall of the tower body (1) below the first discharge hole (105), a second discharge hole (106) is provided on the inner wall of the tower body (1) corresponding to the heavy phase collection chamber (103), the first discharge hole (105) and the second discharge hole (106) are respectively located on both sides of the tower body (1), a heavy phase outlet (17) is provided on the outer wall of the tower body (1) corresponding to the heavy phase collection chamber (103), a second weir plate (18) is fixedly installed on the inner wall of the tower body (1) below the second discharge hole (106), and a baffle plate (19) is fixedly installed on the inner wall of the tower body (1) between the first weir plate (16) and the second weir plate (18), wherein the cross section of the baffle plate (19) is L-shaped.

8. The copper-manganese co-extraction process for wet comprehensive recovery according to claim 5, characterized in that: The reflux mixing tube (6) comprises a first tube body (20), a spoiler (21) and a second tube body (22), wherein the first tube body (20), the spoiler (21) and the second tube body (22) are coaxially arranged, the first tube body (20) is fixedly connected to the bottom of the partition (4), the second tube body (22) is fixedly connected to the bottom of the tower body (1), and the spoiler (21) comprises an annular seat (23), the upper and lower sides of the annular seat (23) are rotatably connected to the first tube body (20) and the second tube body (22) respectively. At the same time, the annular seat (23) has the same inner and outer diameters as the first tube body (20) and the second tube body (22); a plurality of first spoiler blades (24) are fixedly installed on the inner wall of the annular seat (23); the middle of the first spoiler blades (24) is fixedly connected to the drive shaft (5); a plurality of second spoiler blades (25) are fixedly installed on the outer wall of the annular seat (23); the first spoiler blades (24) and the second spoiler blades (25) are arranged in an annular array; and a plurality of reflux holes (26) are opened at the lower end of the second tube body (22).

Images