CN114275945B - Copper recovery device and process - Google Patents
Copper recovery device and process Download PDFInfo
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- CN114275945B CN114275945B CN202111630453.9A CN202111630453A CN114275945B CN 114275945 B CN114275945 B CN 114275945B CN 202111630453 A CN202111630453 A CN 202111630453A CN 114275945 B CN114275945 B CN 114275945B
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000010949 copper Substances 0.000 title claims abstract description 79
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 79
- 238000011084 recovery Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title abstract description 29
- 230000008569 process Effects 0.000 title description 10
- 238000000909 electrodialysis Methods 0.000 claims abstract description 105
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 93
- 238000001728 nano-filtration Methods 0.000 claims abstract description 58
- 239000012528 membrane Substances 0.000 claims abstract description 39
- 230000000903 blocking effect Effects 0.000 claims abstract description 33
- 238000011033 desalting Methods 0.000 claims abstract description 9
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 8
- 239000007788 liquid Substances 0.000 claims description 96
- 239000013505 freshwater Substances 0.000 claims description 30
- 238000000926 separation method Methods 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 238000004064 recycling Methods 0.000 claims description 8
- 238000002955 isolation Methods 0.000 claims description 6
- 238000010612 desalination reaction Methods 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract description 23
- 229910001431 copper ion Inorganic materials 0.000 abstract description 23
- 239000003014 ion exchange membrane Substances 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 239000010842 industrial wastewater Substances 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 230000005684 electric field Effects 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 239000012141 concentrate Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 239000011888 foil Substances 0.000 description 7
- 238000004381 surface treatment Methods 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 238000009388 chemical precipitation Methods 0.000 description 4
- 239000011889 copper foil Substances 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000011550 stock solution Substances 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000011272 standard treatment Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to the field of heavy metal copper ion industrial wastewater treatment, and discloses a copper recovery device and a copper recovery process, wherein the copper recovery device comprises a nanofiltration system and an electrodialysis system; the nanofiltration system receives the second-stage reverse osmosis concentrated water and then enters an electrodialysis system, the special performance of an ion exchange membrane is combined under the action of an electric field force, copper ions enter a concentration chamber through an anode membrane, and then the copper ions are trapped in the concentration chamber due to the blocking of a cathode membrane; along with the extension of the running time of the electrodialysis device, the concentration of copper ions in the desalting chamber is gradually reduced, the concentration of copper ions in the concentrating chamber is continuously increased, and finally the concentration is more than 50 g/L; the invention adopts the combination technology of the membrane method and the electrodialysis, can directly recycle copper ions, and reduces the generation of metallic copper.
Description
Technical Field
The invention relates to the field of heavy metal copper ion industrial wastewater treatment, in particular to a copper recovery device and a copper recovery process.
Background
The production process of the electrolytic copper foil is divided into four steps in total, namely copper dissolution, foil production, liquid manufacturing and surface treatment:
dissolving copper, namely dissolving copper materials into copper sulfate solution in a copper dissolving tank by utilizing sulfuric acid;
a raw foil, in which a copper sulfate solution in a copper dissolving process is fed to an electrolytic bath in a raw foil process, and a copper foil is deposited on a cathode roll by an electrochemical reaction, and this part of the copper foil is called a raw foil or a raw foil because it has not been subjected to a surface treatment;
making liquid, namely providing electrolyte with a corresponding process range for a surface treatment workshop;
surface treatment, namely coiling and conveying the raw foil on a raw foil machine to a surface treatment machine in a surface treatment process, and finishing the surface treatment after the steps of activation, coarsening, sealing treatment, heat-resistant barrier layer, oxidation-resistant layer, organification, drying and the like; finally, checking and packaging to obtain the finished product.
In the whole electrolytic copper foil production process, a large amount of pure water is required to be used for production, flushing equipment and the like, so that a large amount of copper-containing industrial wastewater is generated, and copper ions in the wastewater are required to be separated out for discharging. At present, the main treatment methods of copper-containing wastewater in the market comprise a chemical precipitation method, an ion exchange method and an electrolytic method, and no matter which method needs to be put into manual labor to carry out frequent dosing, cleaning and other operations, the method can not meet the economic and environmental benefits, and can have a full-automatic operation mode and be stably implemented for a long time.
(1) Ion exchange method: the method for separating the ion exchange resin by utilizing the exchange of the ion exchange resin and the ion in the solution is widely used in the field of water treatment, and the ion exchange resin has high performance requirement and high treatment cost in most cases by combining a chemical precipitation method.
(2) Chemical precipitation: the PH of the waste liquid is adjusted by adding sodium hydroxide or calcium hydroxide into the copper-containing waste water, copper ions are precipitated in the form of hydroxide, copper ions are separated out in the form of large precipitate under the action of a flocculating agent, and then solid-liquid separation is realized through filtration. When copper-containing wastewater is treated by a chemical precipitation method, copper ions finally exist in the form of sludge, the purpose of recycling copper ions cannot be achieved, and the treatment of the copper ion-containing sludge can only be carried out by a special recycling enterprise.
(3) Electrolytic method: copper ions in the solution are deposited on the cathode plate under the conditions of high flow rate and high current density, and after a certain amount of copper ions are reached, the cathode plate is taken out to strip copper out and directly serve as copper material for recycling.
Disclosure of Invention
In order to solve the technical problems, the invention provides a copper recovery device and a copper recovery process.
In order to solve the technical problems, the invention adopts the following technical scheme:
a copper recovery device, comprising a nanofiltration system and an electrodialysis system; the nanofiltration system comprises:
the RO collecting water tank is communicated with the water inlet end of the second-stage reverse osmosis concentrated water and the concentrated water outlet end of the nanofiltration device;
the nanofiltration device is characterized in that the water inlet end is communicated with the water outlet end of the RO collecting water tank, and the water outlet end comprises a fresh water outlet end and a concentrated water outlet end;
the copper-containing reuse water tank is communicated with the fresh water outlet end of the nanofiltration device;
the copper-containing concentrated solution tank is communicated with a concentrated water outlet end of the nanofiltration device;
an electrodialysis system comprising:
copper collection water tank;
the electrodialysis device comprises a concentration chamber, a desalination chamber, a polar liquid chamber and a liquid isolation chamber;
the water inlet end of the electrodialysis fresh water tank is communicated with the water outlet end of the copper-containing concentrated liquid tank, and the water outlet end is communicated with a desalting chamber of the electrodialysis device;
the water inlet end of the electrodialysis concentration water tank is communicated with the concentration chamber of the electrodialysis device, and the water outlet end of the electrodialysis concentration water tank is communicated with the copper collection water tank;
an electrodialysis polar liquid box for holding the polar liquid and communicated with a polar liquid chamber of the electrodialysis device;
and the electrodialysis blocking liquid box is used for containing blocking liquid and is communicated with a blocking liquid chamber of the electrodialysis device.
Further, the nanofiltration device comprises a primary nanofiltration component and a secondary nanofiltration component; the first-stage nanofiltration component and the second-stage nanofiltration component comprise a plurality of nanofiltration membranes which are connected in parallel, and the first-stage nanofiltration component and the second-stage nanofiltration component are connected in series.
Further, the nanofiltration membrane is made of polyamide.
Further, the electrodialysis device comprises a cathode plate, an anode plate and a membrane stack; the polar liquid chamber and the liquid blocking chamber are symmetrically arranged between the cathode plate and the anode plate and are sequentially arranged from outside to inside, and the membrane stack is positioned between the two liquid blocking chambers; the membrane stack comprises a plurality of cathode membranes and anode membranes which are repeatedly stacked along the direction from the cathode plate to the anode plate, and the concentration chambers and the desalting chambers are alternately arranged between the cathode membranes and the anode membranes.
Further, the liquid blocking chamber comprises a first liquid blocking chamber and a second liquid blocking chamber; the electrodialysis separation liquid box comprises a first electrodialysis separation liquid box communicated with the first separation liquid chamber and a second electrodialysis separation liquid box communicated with the second separation liquid chamber.
Further, the electrode liquid is dilute sulfuric acid concentrated liquid with the mass fraction of 2% -3%.
Further, the blocking liquid is dilute sulfuric acid concentrated liquid with the mass fraction of 2% -3%.
Recovery process of copper recovery device, wherein the inflow rate of secondary reverse osmosis concentrated water of RO collecting water tank is 15m 3 /h; the fresh water flow of the nanofiltration device is 7.2m 3 And/h, fresh water returns to the copper-containing recycling water pool, and the concentrated water flow is 7.8m 3 /h, 7m 3 Return RO collecting tank per hour, 0.8m 3 H, entering a copper-containing concentrated solution tank;
the electrodialysis fresh water tank is used for receiving water in the copper-containing concentrated solution tank and supplying liquid to a desalting chamber of the electrodialysis device; the flow rate of the electrodialysis fresh water tank is 10-15m 3 /h；
The flow rate of the electrodialysis concentrated water tank is 10-15m 3 And (h) after the concentration of the solution reaches 50g/L, the solution enters a copper collection water tank;
the electrodialysis pole liquid box is used for circularly supplying electrode liquid to pole liquid chamber of electrodialysis device, and the flow rate of the electrodialysis pole liquid box is 1-3m 3 /h；
ElectroosmosisThe separation liquid tank is used for circularly supplying separation liquid to a separation liquid chamber of the electrodialysis device; the flow rate of the electrodialysis separation liquid tank is 1-3m 3 /h。
Compared with the prior art, the invention has the beneficial technical effects that:
1. the nanofiltration system of the invention receives the second-stage reverse osmosis concentrated water and then enters an electrodialysis system, the special performance of an ion exchange membrane is combined under the action of an electric field force, copper ions enter a concentration chamber through an anode membrane, then the copper ions are trapped in the concentration chamber due to the blocking of a cathode membrane, the concentration of the copper ions in a desalting chamber is gradually reduced along with the extension of the operation time of an electrodialysis device, the concentration of the copper ions in the concentration chamber is continuously increased, and finally the concentration of the copper ions is more than 50 g/L; the invention adopts the combination technology of the membrane method and the electrodialysis, can directly recycle copper ions, and reduces the generation of metallic copper;
2. the invention occupies small area, fully utilizes the original equipment and maximizes the utilization of resources; full-automatic control and stable operation; the structure and principle are simple and easy to understand.
3. The invention adopts the process flow of the nanofiltration system-electrodialysis system, and can keep the performance and the service life of the membrane for a long time and save the cost compared with other membrane method copper recovery methods; compared with the electrolytic method for recycling copper, the method can directly recycle copper ions in the copper-containing reuse water, thereby avoiding the complexity of subsequent treatment for recycling metallic copper; compared with a chemical method for recovering copper, the method reduces the addition of the chemical agent and the wastewater treatment cost.
Drawings
FIG. 1 is a process flow diagram of a nanofiltration system of the present invention;
FIG. 2 is a process flow diagram of the electrodialysis system of the invention;
fig. 3 is a schematic structural view of an electrodialysis device according to the invention.
Detailed Description
A preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings.
The invention is mainly realized by a nanofiltration system and an electrodialysis system.
As shown in fig. 1, the nanofiltration system comprises: RO collecting water tank 1, nanofiltration device 2, copper-containing reuse water tank and copper-containing concentrate tank 3; the nanofiltration system receives second-stage reverse osmosis concentrated water, fresh water concentrated by the nanofiltration device 2 enters a copper-containing reuse water tank, the concentrated water is divided into two parts, one part of concentrated water enters an RO collecting water tank 1, and the other part of concentrated water enters a copper-containing concentrated liquid tank 3.
The nanofiltration device 2 comprises a primary nanofiltration component and a secondary nanofiltration component; the primary nanofiltration component and the secondary nanofiltration component comprise a plurality of nanofiltration membranes 21 which are connected in parallel, and the primary nanofiltration component and the secondary nanofiltration component are connected in series. That is, the nanofiltration membrane 21 adopts a cross-flow filtration mode, so that the blocking phenomenon generated in the dead-end filtration process can be avoided, the pollution of the nanofiltration membrane 21 is reduced, and the higher membrane permeation flux is maintained.
The nanofiltration membrane 21 is preferably made of polyamide.
The water inflow rate of the nanofiltration system is set to be 15m 3 /h; the fresh water flow rate of the nanofiltration device 2 is 7.2m 3 And/h, fresh water returns to the copper-containing recycling water pool, and the concentrated water flow is 7.8m 3 /h, 7m 3 Return/h RO collecting tank 1,0.8m 3 And/h into a copper-containing concentrate tank 3.
As shown in fig. 2, the electrodialysis system comprises an electrodialysis device 4, an electrodialysis fresh water tank 5, an electrodialysis concentrate tank 7, an electrodialysis pole liquid tank 6, an electrodialysis separation liquid tank, a rectifier and a copper collection water tank 9. The concentrated solution concentrated by the nanofiltration system enters an electrodialysis concentrate tank 7 and an electrodialysis fresh water tank 5 through a copper-containing concentrate tank 3, the electrodialysis fresh water tank 5 provides raw water for an electrodialysis device 4, after the concentration of the electrodialysis device 4, fresh water is reduced to a certain concentration, the raw water is discharged into a copper-containing wastewater pool for standard treatment, the concentrated water enters the electrodialysis concentrate tank 7, and when the concentration of the electrodialysis concentrate tank 7 reaches more than 50g/L, the concentrated water is automatically discharged into a copper collecting tank 9, and the copper collecting tank 9 enters a copper dissolving tank for use.
As shown in fig. 3, a cathode plate 42 and an anode plate 41 are arranged in the electrodialysis device 4, a membrane stack is arranged between the anode plate 41 and the cathode plate 42, and a polar liquid chamber 43, a second liquid blocking chamber 44 and a first liquid blocking chamber 45 are symmetrically arranged between the anode plate 41 and the membrane stack and between the cathode plate 42 and the membrane stack; the polar liquid chamber 43 is located outside, the first liquid blocking chamber 45 is located inside, and the second liquid blocking chamber 44 is located between the polar liquid chamber 43 and the first liquid blocking chamber 45.
In the invention, the direction approaching the membrane stack is the inner direction and the direction separating from the membrane stack is the outer direction.
The stack is composed of a plurality of anode films 46 and cathode films 47 alternately, one of the stack closest to the anode plate 41 is the anode film 46, and one of the stack closest to the cathode plate 42 is the cathode film 47. A special partition plate is filled between the adjacent anode film 46 and the cathode film 47 in the film stack, so that a staggered concentration chamber and a staggered desalination chamber are formed, namely, a concentration chamber, a desalination chamber, a concentration chamber and a desalination chamber … … alternate structure is formed; the concentrated outdoor unit is connected with the electrodialysis concentrated water tank 7, the desalted outdoor unit is connected with the electrodialysis fresh water tank 5, the first isolation liquid chamber 45 is connected with the first electrodialysis isolation liquid tank 81, the second isolation liquid chamber 44 is connected with the second electrodialysis isolation liquid tank 82, and the polar liquid chamber 43 is connected with the electrodialysis polar liquid tank 6.
The cathode film 47 and the anode film 46 in the invention belong to ion exchange films, are organic polymer materials formed in a sheet shape, and contain ion exchange groups such as sulfonic acid, quaternary ammonium and the like; negatively charged functional groups (typically sulfonic acids) are immobilized in the cation exchange membrane; the anion exchange membrane has immobilized therein positively charged functional groups (typically quaternary ammonium); ions of the same polarity as the fixed charge are repelled from passing through the ion exchange membrane, and only ions of the opposite polarity to the fixed charge pass through the ion exchange membrane, so that the anode membrane 46 is permeable to cations and the cathode membrane 47 is permeable to anions.
The electrodialysis fresh water tank 5 is used for receiving water in the copper-containing concentrated solution tank 3 and supplying liquid to the desalting chamber of the electrodialysis device 4, and receiving desalted water at the same time; the flow rate of the electrodialysis fresh water tank 5 is 10-15m 3 /h。
The electrodialysis concentrate tank 7 is used for circularly supplying liquid to the concentration chamber of the electrodialysis device 4, and the flow is 10-15m 3 And/h, after the concentration of the solution reaches 50g/L, the solution enters a copper collection water tank 9.
The electrodialysis pole liquor box 6 is used for circularly supplying electrode liquor to the pole liquor chamber 43 of the electrodialysis device 4, and the flow rate of the electrodialysis pole liquor box 6 is 1-3m 3 /h; the electrode liquid is a dilute sulfuric acid solution, and the mass fraction is preferably 2% -3%.
The electrodialysis blocking liquid tank is used for circularly supplying blocking liquid to the blocking liquid chamber of the electrodialysis device 4; the flow rate of the electrodialysis separation liquid tank is 1-3m 3 /h; the blocking liquid comprises dilute sulfuric acid solution, and the mass fraction is preferably 2% -3%.
The rectifier is used to supply direct current to the electrodialysis device 4.
The working principle of the invention is as follows: the copper-containing reuse water is collected into RO collection water tank 1 (copper ion concentration 2g/L-5 g/L) through concentrated water of the secondary reverse osmosis device, and then passes through nanofiltration device 2, fresh water (7.2 m) 3 And/h) returning to the copper-containing reuse water tank, and a large amount of concentrated water (7 m) 3 And/h) returned to RO collecting tank 1, a small amount of concentrate (0.8 m) 3 And/h) entering a copper-containing concentrate tank 3; and then the water in the copper-containing concentrate tank 3 is supplemented to the electrodialysis concentrate tank 7 and the electrodialysis fresh water tank by a pump, and after the water is supplemented, the electrodialysis system current is set and started, and the current is preferably 90-100A. The electrodialysis fresh water tank 5 and the electrodialysis concentrate tank 7 are used for providing stock solution for the electrodialysis device 4; fresh water output by the electrodialysis device returns to a copper-containing reuse water tank, and the concentration of the electrodialysis fresh water tank 5 is lower than 1g and can be automatically discharged; the concentrated water output by the electrodialysis device enters an electrodialysis concentrated water tank 7, and after the copper content of the electrodialysis concentrated water tank 7 reaches 50g/L, the concentrated water is automatically discharged to a copper collecting water tank 9 (5 m) 3 ) Enters a copper dissolving tank for use through a copper collecting water tank 9; then replenishing the stock solution of the copper-containing concentrate tank 3 in the nanofiltration system to 1.5 m, and replenishing the stock solution of the copper-containing concentrate tank 3 to the liquid level of the electrodialysis fresh water tank 5 to 1.2 m; concentrating for 5m 3 The copper collection took 48 hours and all dosing pumps remained on during the entire concentration process.
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 characteristics 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.
Furthermore, it should be understood that although the present disclosure describes embodiments, not every embodiment is provided with a single embodiment, and that this description is provided for clarity only, and that the disclosure is not limited to specific embodiments, and that the embodiments may be combined appropriately to form other embodiments that will be understood by those skilled in the art.
Claims (5)
1. A recovery process of a copper recovery device is characterized in that: the copper recovery device comprises a nanofiltration system and an electrodialysis system; the nanofiltration system comprises:
the RO collecting water tank is communicated with the water inlet end of the second-stage reverse osmosis concentrated water and the concentrated water outlet end of the nanofiltration device;
the nanofiltration device is characterized in that the water inlet end is communicated with the water outlet end of the RO collecting water tank, and the water outlet end comprises a fresh water outlet end and a concentrated water outlet end;
the copper-containing reuse water tank is communicated with the fresh water outlet end of the nanofiltration device;
the copper-containing concentrated solution tank is communicated with a concentrated water outlet end of the nanofiltration device;
an electrodialysis system comprising:
copper collection water tank;
the electrodialysis device comprises a concentration chamber, a desalination chamber, a polar liquid chamber and a liquid isolation chamber;
the water inlet end of the electrodialysis fresh water tank is communicated with the water outlet end of the copper-containing concentrated liquid tank, and the water outlet end is communicated with a desalting chamber of the electrodialysis device;
the water inlet end of the electrodialysis concentration water tank is communicated with the concentration chamber of the electrodialysis device, and the water outlet end of the electrodialysis concentration water tank is communicated with the copper collection water tank;
an electrodialysis polar liquid box for holding the polar liquid and communicated with a polar liquid chamber of the electrodialysis device;
an electrodialysis blocking liquid box which contains blocking liquid and is communicated with a blocking liquid chamber of an electrodialysis device;
the electrodialysis device comprises a cathode plate, an anode plate and a membrane stack; the polar liquid chamber and the liquid blocking chamber are symmetrically arranged between the cathode plate and the anode plate and are sequentially arranged from outside to inside, and the membrane stack is positioned between the two liquid blocking chambers; the membrane stack comprises a plurality of cathode membranes and anode membranes which are repeatedly stacked along the direction from the cathode plate to the anode plate, and the concentration chambers and the desalting chambers are alternately arranged between the cathode membranes and the anode membranes;
the electrode liquid is dilute sulfuric acid concentrated liquid with mass fraction of 2% -3%;
the inflow rate of the secondary reverse osmosis concentrated water of the RO collecting water tank is 15m 3 /h; the fresh water flow of the nanofiltration device is 7.2m 3 And/h, fresh water returns to the copper-containing recycling water pool, and the concentrated water flow is 7.8m 3 /h, 7m 3 Return RO collecting tank per hour, 0.8m 3 H, entering a copper-containing concentrated solution tank;
the electrodialysis fresh water tank is used for receiving water in the copper-containing concentrated solution tank and supplying liquid to a desalting chamber of the electrodialysis device; the flow rate of the electrodialysis fresh water tank is 10-15m 3 /h；
The flow rate of the electrodialysis concentrated water tank is 10-15m 3 And (h) after the concentration of the solution reaches 50g/L, the solution enters a copper collection water tank;
the electrodialysis pole liquid box is used for circularly supplying electrode liquid to pole liquid chamber of electrodialysis device, and the flow rate of the electrodialysis pole liquid box is 1-3m 3 /h；
The electrodialysis blocking liquid box is used for circularly supplying blocking liquid to a blocking liquid chamber of the electrodialysis device; the flow rate of the electrodialysis separation liquid tank is 1-3m 3 /h。
2. The recovery process of the copper recovery apparatus according to claim 1, wherein: the nanofiltration device comprises a primary nanofiltration component and a secondary nanofiltration component; the first-stage nanofiltration component and the second-stage nanofiltration component comprise a plurality of nanofiltration membranes which are connected in parallel, and the first-stage nanofiltration component and the second-stage nanofiltration component are connected in series.
3. The recovery process of the copper recovery apparatus according to claim 2, wherein: the nanofiltration membrane is made of polyamide.
4. The recovery process of the copper recovery apparatus according to claim 1, wherein: the liquid blocking chamber comprises a first liquid blocking chamber positioned at the inner side and a second liquid blocking chamber positioned at the outer side; the electrodialysis separation liquid box comprises a first electrodialysis separation liquid box communicated with the first separation liquid chamber and a second electrodialysis separation liquid box communicated with the second separation liquid chamber.
5. The recovery process of the copper recovery apparatus according to claim 1, wherein: the blocking liquid is dilute sulfuric acid concentrated liquid with mass fraction of 2% -3%.
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| CN202111630453.9A CN114275945B (en) | 2021-12-28 | 2021-12-28 | Copper recovery device and process |
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| CN202111630453.9A CN114275945B (en) | 2021-12-28 | 2021-12-28 | Copper recovery device and process |
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| CN101830587B (en) * | 2010-04-26 | 2012-11-21 | 烟台大学 | Process and device for processing heavy metal wastewater |
| CN106345304A (en) * | 2016-11-16 | 2017-01-25 | 中国科学院青海盐湖研究所 | Cathodic solution protection type electrodialysis device |
| CN210795993U (en) * | 2019-10-31 | 2020-06-19 | 惠州联合铜箔电子材料有限公司 | Electrolytic copper foil surface cleaning wastewater recycling system device |
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