阅读说明：本技术 一种硝酸铜废水铜回收方法 (Copper recovery method for copper nitrate wastewater ) 是由 黄文涛 李再强 梁民 汪前程 于 2020-11-05 设计创作，主要内容包括：本发明公开了一种硝酸铜废水铜回收方法,具体涉及铜回收领域,包括以下步骤：所述电解槽的内腔底部设置有阳离子膜,阳极为钛板,阴极为铜板,所述阳离子膜将电解槽内隔成阳极区和阴极区；将硝酸铜废水导入电解槽内的阳极区,将硫酸溶液导入到阴极区；并在电解槽内对硝酸铜废水进行搅拌,同时给两电极通直流电进行电解。本发明通过使用阳离子膜将电解槽隔开,阳极区为硝酸铜溶液,阴极区为硫酸溶液,阳极采用钛板,阴极采用铜板,铜离子被电解沉积在铜板上,阳极区增加了阳极溶液的酸度,使阳极区硝酸铜溶液脱铜后可以作为腐蚀铜溶液调配的原材料,进而实现硝酸铜废液的循环利用。(The invention discloses a copper recovery method for copper nitrate wastewater, and particularly relates to the field of copper recovery, which comprises the following steps: the bottom of the inner cavity of the electrolytic cell is provided with a cationic membrane, the anode is a titanium plate, the cathode is a copper plate, and the inside of the electrolytic cell is divided into an anode area and a cathode area by the cationic membrane; leading the copper nitrate wastewater into an anode region in an electrolytic cell, and leading a sulfuric acid solution into a cathode region; and stirring the copper nitrate wastewater in an electrolytic bath, and simultaneously electrifying the two electrodes with direct current for electrolysis. The electrolytic tank is separated by using the cationic membrane, the anode area is a copper nitrate solution, the cathode area is a sulfuric acid solution, the anode is a titanium plate, the cathode is a copper plate, copper ions are electrolytically deposited on the copper plate, the acidity of the anode solution is increased in the anode area, so that the copper nitrate solution in the anode area can be used as a raw material for blending a corrosive copper solution after being decoppered, and further the recycling of the copper nitrate waste liquid is realized.)

1. A method for recovering copper from copper nitrate wastewater is characterized by comprising the following steps: the method comprises the following steps:

s1: the anode is a titanium plate, the cathode is a copper plate, the bottom of the inner cavity of the electrolytic cell is provided with a cation membrane, the cation membrane divides the inside of the electrolytic cell into an anode region and a cathode region, the anode is positioned in the anode region, and the cathode is positioned in the cathode region;

s2: leading the copper nitrate wastewater into an anode region in an electrolytic cell, and leading a sulfuric acid solution into a cathode region;

s3: stirring the copper nitrate wastewater in the anode area in an electrolytic tank, and simultaneously electrifying direct current to the two electrodes for electrolysis, so that copper ions in the copper nitrate wastewater in the anode area penetrate through a cation membrane to be deposited on a copper cathode plate, and a hydrogen ion bed cation membrane in the cathode area enters the anode area, thereby increasing the acidity of the solution in the anode area;

s4: connect trachea and outside air compressor, air compressor carries out gaseous stirring to copper nitrate waste water from the blowout in the gas pocket with outside air compression intake pipe.

2. The method for recovering copper from copper nitrate wastewater according to claim 1, characterized in that: the cation membrane is a cation exchange membrane, and the cation exchange membrane is prepared by adopting a melt extrusion casting film forming process or a solution casting film forming process, and carrying out acid washing, water washing and drying.

3. The method for recovering copper from copper nitrate wastewater according to claim 1, characterized in that: in the step S3, the stirring speed is 100-200r/min, and the stirring time is 5-10 minutes.

4. The method for recovering copper from copper nitrate wastewater according to claim 1, characterized in that: the electrolysis temperature in the steps S3 and S4 is 30-35 ℃.

5. The method for recovering copper from copper nitrate wastewater according to claim 1, characterized in that: the electrolysis temperature in step S2 was 40 ℃.

6. The method for recovering copper from copper nitrate wastewater according to claim 1, characterized in that: the concentration of the sulfuric acid in the step S2 is 210 g/L.

Technical Field

The invention relates to the technical field of copper recovery, in particular to a method for recovering copper from copper nitrate wastewater.

Background

Copper nitrate wastewater widely exists in the fields of electroplating and powder metallurgy, and at present, a precipitation-electrolysis method and a replacement-electrolysis method can be generally adopted for a method for recovering copper from copper nitrate wastewater.

The method comprises the steps of adding a sodium carbonate solution into the copper nitrate wastewater, precipitating copper ions and the like, filtering the precipitate, cleaning, drying, reducing by hydrogen, smelting and casting the reduced blister copper into a plate, and then carrying out electrolytic purification.

The method comprises the steps of spraying iron powder into the copper nitrate wastewater, displacing copper ions, cleaning, drying, smelting, casting into a plate, and then carrying out electrolytic purification.

The existing method for recovering copper nitrate by electrodeposition still has more defects in practical use, such as complicated recovery process, long flow and poor recycling effect on copper nitrate waste liquid.

Disclosure of Invention

In order to overcome the above defects in the prior art, the embodiment of the invention provides a method for recovering copper from copper nitrate wastewater, and the problems to be solved by the invention are as follows: the existing method for recovering copper nitrate by electrodeposition copper has the disadvantages of complicated recovery process, long flow and poor recycling effect on copper nitrate waste liquid.

In order to achieve the purpose, the invention provides the following technical scheme: a method for recovering copper from copper nitrate wastewater comprises the following steps:

s1: the anode is a titanium plate, the cathode is a copper plate, the bottom of the inner cavity of the electrolytic cell is provided with a cation membrane, the cation membrane divides the inside of the electrolytic cell into an anode region and a cathode region, the anode is positioned in the anode region, and the cathode is positioned in the cathode region;

s2: leading the copper nitrate wastewater into an anode region in an electrolytic cell, and leading a sulfuric acid solution into a cathode region;

s3: stirring the copper nitrate wastewater in the anode area in an electrolytic tank, and simultaneously electrifying direct current to the two electrodes for electrolysis, so that copper ions in the copper nitrate wastewater in the anode area penetrate through a cation membrane to be deposited on a copper cathode plate, and a hydrogen ion bed cation membrane in the cathode area enters the anode area, thereby increasing the acidity of the solution in the anode area;

s4: connect trachea and outside air compressor, air compressor carries out gaseous stirring to copper nitrate waste water from the blowout in the gas pocket with outside air compression intake pipe.

In a preferred embodiment, the cation exchange membrane is a cation exchange membrane, and the cation exchange membrane is prepared by adopting a melt extrusion casting film forming process or a solution casting film forming process, and is subjected to acid washing, water washing and drying.

In a preferred embodiment, in the step S3, the stirring speed is 100-200r/min, and the stirring time is 5-10 minutes.

In a preferred embodiment, the electrolysis temperature in the steps S3 and S4 is 30-35 ℃.

In a preferred embodiment, the electrolysis temperature in step S2 is 40 ℃.

In a preferred embodiment, the concentration of sulfuric acid in the step S2 is 210 g/L.

The invention has the technical effects and advantages that:

1. the electrolytic tank is partitioned by using the cationic membrane, the anode area is a copper nitrate solution, the cathode area is a sulfuric acid solution, the anode is a titanium plate, the cathode is a copper plate, so that anode copper ions can enter the cathode area through the cationic membrane to be electrolytically deposited on the copper plate, and cathode hydrogen ions enter the anode area through the cationic membrane to increase the acidity of the anode solution, so that the anode area copper nitrate solution can be used as a raw material for blending a corrosive copper solution after being decoppered, and the recycling of the copper nitrate waste liquid is realized;

2. in the invention, the copper nitrate wastewater is stirred by gas in the electrolytic tank during the electrolytic process, so that the copper nitrate wastewater is in a turnover state, and H in the solution is reduced⁺Concentration of H can be prevented⁺、NO₃ ^-Compared with the prior art, the anode for corroding the titanium plate has the advantage of further avoiding the anode titanium plate from being quickly corroded and dissolved.

Drawings

FIG. 1 is a schematic front view of the overall structure of the present invention;

FIG. 2 is a schematic top view of the reciprocating mechanism of the present invention.

The reference signs are: the device comprises an electrolytic cell 1, an anode plate 11, a cathode plate 12, a cation membrane 13, a gas pipe 2, a gas hole 21, a first motor 3, a rocker 31, a reciprocating mechanism 4, a movable plate 41, a sliding chute 42, a sliding block 43, a connecting rod 44, a fixed sleeve 45, a second motor 5 and a stirring shaft 51.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The method for recovering copper from copper nitrate wastewater provided by the embodiment of the invention comprises the following steps:

s1: the anode is a titanium plate, the cathode is a copper plate, the bottom of the inner cavity of the electrolytic cell is provided with a cation membrane, the cation membrane divides the inside of the electrolytic cell into an anode region and a cathode region, the anode is positioned in the anode region, and the cathode is positioned in the cathode region;

s2: leading the copper nitrate wastewater into an anode region in an electrolytic cell, and leading a sulfuric acid solution into a cathode region;

s3: stirring the copper nitrate wastewater in the anode area in an electrolytic tank, and simultaneously electrifying direct current to the two electrodes for electrolysis, so that copper ions in the copper nitrate wastewater in the anode area penetrate through a cation membrane to be deposited on a copper cathode plate, and a hydrogen ion bed cation membrane in the cathode area enters the anode area, thereby increasing the acidity of the solution in the anode area;

s4: connect trachea and outside air compressor, air compressor carries out gaseous stirring to copper nitrate waste water from the blowout in the gas pocket with outside air compression intake pipe.

As shown in fig. 1 and 2, the implementation scenario specifically includes: electrolysis using a cationic membrane 13The tank 1 is internally partitioned, the anode area is copper nitrate solution, the cathode area is sulfuric acid solution, the anode is titanium plate, the cathode is copper plate, thus anode copper ions can enter the cathode area through the cation membrane 13 to be electrolytically deposited on the copper plate, and cathode hydrogen ions enter the anode area through the cation membrane 13 to increase the acidity of the anode solution, so that the anode copper nitrate solution can be used as a raw material for blending corrosive copper solution after decoppering, and the recycling of copper nitrate waste liquid is realized; in the electrolytic process, the copper nitrate wastewater is stirred in the electrolytic tank 1 to make the copper nitrate wastewater in a turning state, and H generated by electrode reaction generated at the cathode⁺With NO₃ ^-The combination corrodes the titanium plate of the anode, and after gas stirring, a chemical reaction occurs: 4H⁺+4NO₃ ^-＝4NO₂↑+O₂↑+2H₂O, reduction of H in solution⁺Concentration of H can be prevented⁺、NO₃ ^-Corroding the titanium plate anode; and through gas stirring, make the ion concentration in the electrolysis trough even, be favorable to improving the recovery efficiency of electrodeposition, add reducing substance in order to reduce the redox potential of electrolyte, be favorable to guaranteeing electrolytic copper's efficiency, this embodiment has specifically solved the loaded down with trivial details of process that exists among the prior art, the flow is long, the problem poor to the cyclic utilization effect of copper nitrate waste liquid.

The cation membrane is a cation exchange membrane, and the cation exchange membrane is prepared by adopting a melt extrusion casting film forming process or a solution casting film forming process, and carrying out acid washing, water washing and drying.

In the step S3, the stirring speed is 100-200r/min, and the stirring time is 5-10 minutes.

The electrolysis temperature in the steps S3 and S4 is 30-35 ℃.

The electrolysis temperature in step S2 was 40 ℃.

The concentration of the sulfuric acid in the step S2 is 210 g/L.

The method for recovering copper from copper nitrate wastewater uses an electrolytic tank 1, an anode plate 11 and a cathode plate 12 are arranged in the electrolytic tank 1, wherein the anode plate 11 is a titanium plate, the cathode plate 12 is a copper plate, a cation membrane 13 is fixedly embedded between two side walls of the bottom of the inner cavity of the electrolytic bath 1, the inside of the electrolytic tank 1 is divided into an anode area and a cathode area by the cation membrane 13, one side of the electrolytic tank 1 is provided with an air pipe 2 in a penetrating way, the pipe wall of the gas pipe 2 in the electrolytic bath 1 is provided with a plurality of uniformly distributed gas holes 21, and one end of the air pipe 2 positioned outside the electrolytic tank 1 is connected with an air compressor, the top of the electrolytic tank 1 is fixedly connected with a first motor 3, an output shaft of the first motor 3 movably penetrates through the top of the electrolytic tank 1, and the output shaft end of the first motor 3 is fixedly connected with a rocker 31, and the top of the inner cavity of the electrolytic cell 1 is provided with a reciprocating mechanism 4.

The reciprocating mechanism 4 in the using device in the method for recovering copper in copper nitrate wastewater comprises a movable plate 41, a sliding groove 42 is formed in the top of the movable plate 41 in a penetrating mode, a sliding block 43 is connected to the inside of the sliding groove 42 in a sliding mode, the top of the sliding block 43 is hinged to one end, away from an output shaft of a first motor 3, of a rocker 31, a connecting rod 44 is fixedly connected to one side of the movable plate 41, a second motor 5 is fixedly connected to the bottom of one end, away from the movable plate 41, of the connecting rod 44, an output shaft 51 of the second motor 5 is fixedly connected to a stirring shaft through a coupler, a fixed sleeve 45 is fixedly connected to the top of an inner cavity of the.

As shown in fig. 1 and 2, the implementation scenario specifically includes: in the time of the in-service use, through setting up reciprocating mechanism 4 and (mixing) shaft 51, first motor 3 drives rocker 31 and rotates, rocker 31 makes slider 43 still make fly leaf 41 do the reciprocating motion of making a round trip in the left and right sides orientation when sliding in spout 42, and then drive (mixing) shaft 51 when being stirring motion, can also remove, the homogeneity of each ion concentration in electrolysis trough 1 has been guaranteed, be favorable to improving recovery efficiency, and through stirring, make the ion concentration in electrolysis trough 1 even, reduce the concentration difference in electrolysis trough 1, accelerate the removal of ion, improve the electrolytic power of low concentration solution, make the electrolysis process still can go on under the condition of low concentration at copper nitrate waste water, this embodiment has specifically solved the problem that the copper nitrate waste water recovery method recovery efficiency that exists among the prior art is low and does not change in waste water low concentration recovery.

In summary, the following steps: according to the invention, the strong oxidant is added before electrodeposition, and the oxidant is used for carrying out oxidation treatment on the anode titanium plate to change the surface of the anode titanium plate into an inactive state, so that the corrosion speed of the anode titanium plate by copper nitrate wastewater can be effectively delayed, and the service life of the titanium plate in the use of electrodeposition copper is further prolonged; in the electrolytic process, the copper nitrate wastewater is stirred in the electrolytic tank 1 to make the copper nitrate wastewater in a turning state, and H generated by electrode reaction generated at the cathode⁺With NO₃ ^-The combination will corrode the titanium plate of the anode, and after gas agitation, the H content in the solution is reduced⁺Concentration of H can be prevented⁺、NO₃ ^-And corroding the titanium plate anode.

And finally: the above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that are within the spirit and principle of the present invention are intended to be included in the scope of the present invention.